Comprehensive Organometallic Chemistry || η3-Allylnickel Complexes

37.6

773-Allylnickel ComplexesP. W. JOLLY

Max-Planck-lnstitut fur Kohlenforschung, Miilheim a.d. Ruhr

37.6.1 INTRODUCTION 14537.6.2 BIS(?73-ALLYL)NICKEL COMPLEXES 145

37.6.2.1 Preparation 14537.6.2.2 Reactions 14837.6.2.3 Structure and Bonding 149

37.6.3 BIS(i73-ALLYL)NICKEL LIGAND COMPLEXES 15237.6.4 [{NiX(7?3-ALLYL)}2] COMPLEXES 156

37.6.4.1 Preparation 15637.6.4.2 Reactions 160

37.6.4.2.1 In which the rj3-allyl group is displaced 16037.6.4.2.2 In which the allyl group remains intact 161

37.6.4.3 Structure and Bonding 16137.6.5 [NiX(L)(?73-ALLYL)] COMPLEXES 163

37.6.5.1 Preparation 16337.6.5.2 Reactions 167

37.6.5.2.1 In which the r)3-allyl group is displaced 16737.6.5.3 Structure and Bonding 169

37.6.6 [NiXLM(?73-ALLYL)] COMPLEXES (« = 2, 3) 17237.6.7 [Ni(?73-ALLYL)(T7-CYCLOPENTADIENYL)] COMPLEXES 17437.6.8 i;3-CYCLOPROPENYLNICKEL COMPLEXES 177REFERENCES 179

37.6.1 INTRODUCTION

The 773-allylnickel complexes are involved, as intermediates, in many of the nickel-catalyzedtransformations of dienes and have been investigated in considerable detail. We have devotedseparate Sections to the following complexes: [Ni(r/3-allyl)2], [{NiX(773-allyl)}2], [NiXLn(r?

3-allyl)]and [Ni(?73-allyl)(?7-cyclopentadienyl)], and these are followed by a brief discussion of the related773-cyclopropenyl system. A summary of earlier work and a discussion of the bonding situationis to be found in ref. 1, chapter 6.

37.6.2 BIS(?73-ALLYL)NICKEL COMPLEXES*

37.6.2.1 Preparation

The most commonly used method to prepare the bis(773-allyl)nickel complexes is the reactionof a nickel halide and an allyl Grignard reagent (equations 1, 2).135 '136 Attempts to preparecomplexes containing two different allyl groups generally result in disproportionation (equations3, 4).52 '82 An exception is the reaction leading to the substituted r;3-cyclobutenylnickel complex(1) (equation 5).106

* See Table 1, p. 146.

145

The use of allylsodium reagents instead of a Grignard has been mentioned,104 while satisfactoryyields of substituted bis(?73-allyl)nickel complexes are reported to be formed on reacting the ap-propriate [{NiX(773-allyl)J2] complex with a zinc-copper couple in DMF or HMPT.157 Bis-(r73-indenyl)nickel may be prepared by a related reaction (equation 6). The diamagnetic nature

Table 1 [Ni^-Allylh] Complexes3

rj^-Allyl Group

C3H5a

l-MeC3H4a

l-Pr iC3H4

l-PhC3H4a

2-MeC3H4(19)a

2-Me3SiC3H4

2-PhC3H4

l , l - M e 2 C 3 H 3 ( l l ) a

(+)-pinenyl (21)a

(—)-pinenyll,3-Me2C3H3

a

indenyla

cyclohexenyla

pcycloheptenyla

cyclooctenyla

cyclooctatrienyl (20)a

l,l,3,3-Ph4C3H

Miscellaneous{Ni(r;3,T;3-C8H8)}2] (3)a

JNi(773,T73-PhC8H7)}2]Ni(r;3-Ph3C5H2PEt)2Ni(CH2=CH2)](23)Ni(r?

3-Ph3C5H2PEt)2Ni(C5H8)]Ni(773-Ph3C5H2PEt)2Ni(MeC^CMe)lNi(??3-Ph3C5H2PEt)2Ni(EtC^CEt)]Ni(773-Ph3C5H2PEt)2Ni(PCy3)]Ni(7?

3-Ph3C5H2PEt)2Ni(PC5Ph3H2)]

Ref.

3, 5, 9, 13, 27, 45, 55, 58, 73, 84, 90, 99,107, 110, 117,135,136,154,164

45,84, 110,124,13513513573,84,135, 136,154,16482145135525284,1353313513513513514

Complexes88144183183183183183183

a Earlier work has been discussed and tabulated in ref. 1, pp. 336-342, 376-393.

146 r]3-AIlyInickel Complexes

i M g B rNiCl2 + 2 ^ ^ ^ —*• [Ni(7/3-2-MeC3H4)2] + 2MgBrCl (1)

/ = \ > MgBr

NiBr2 + 2 ([ T - ^ [Ni(7;3-cyclooctatrienyl)2] + 2MgBr2 (2)

2[!NiBr(7?3-(+)-pinenyl))2] + 1 ^ ^ ^ ^ ^ ~2MgBrS 2[Ni(r;3-C3H5)(i73-(+)-pinenyl)] —*

[Ni(7?3-C3H5)2] + [NiO73-(+)-pinenyl)2] (3)

[|NiCl(J;3-2-Me3SiC3H4)!2] + 2 ^ N ^ " M g C 1 _2MgC,2>

[Ni(7;3-C3H5)2] + [Ni(7/3-2-Me3SiC3H4)2] (4)

( Y j C - N i C l 2 ) 2 + 2C3H5MgX "2MgXQ>

(tP'Cl)> * » ^1&Ni-> (5)/A ' \

(1)

rj3-Allylnickel Complexes 147

of this red complex precludes a structure analogous to nickelocene and a 13C NMR spectrum hasconfirmed the structure33 (see ref. 1, p. 432). It is convenient to mention here that the 1,1,3,3-tetraphenylallyl radical reacts with [Ni(cdt)] to give a red-brown diamagnetic complex formulatedas [Ni(iy3-Ph4C3H)2].14

Ni(acac)2 + 2 C JL / + 2UBu -SacaV ( 0 w ^ ~ N i ~ V j f t 3 (6)

A second general preparative method involves disproportionation of [(NiX(773-allyl)J2] complexes(equation 7). In the case where X is halogen, the equilibrium can be displaced in favour of thebis(r73-allyl)nickel complex by dissolving the dimer in a coordinating solvent such as NH3, H2Oor DMF (see ref. 1, p. 337).5'117'136 The hydride, alkyl, alkoxy or acetate derivatives undergospontaneous disproportionation (equations 8, 9).5 '136 Presumably related is the reaction of bis-(cyclooctadiene)nickel with allyl acetate (equation 10).90 Interestingly the disproportionationof [{NiMe(?73-C3H5)}2] leads to the /ra«s-bis(?73-allyl)nickel isomer whereas the reaction involving[fNiMe(773-2-MeC3H4)}2] results in initial formation of the cis isomer.136

[{NiX(773-allyI)}2] ^ [Ni(7/3-allyl)2] + NiX2 (7)

[jNiMe(773-2-MeC3H4)J2] —• [Ni(773-2-MeC3H4)2] + "[NiMe2]" (8)

[{NiOR(773-C3H5)!2] —•* [Ni(7;3-C3H5)2] + Ni(OR)2 (9)

2[Ni(cod)2] + 2 MeCO2CH2CH=CH2 ^ ^ [{NiOCOMe(7?3-C3H5)!2] —•

[Ni(773-C3H5)2] + Ni(OCOMe)2 (10)

A number of bis(?73-allyl)nickel complexes have been isolated from reactions involving dienesand these are discussed below. Reduction of nickel chloride in the presence of pentadiene leadsto formation of bis(pentadienyl)dinickel (2) (equation II).5 9 The crystal structure of (2) is shownon p. 151. The final product of the reaction of cyclooctatetraene with zerovalent nickel is a blackcrystalline material which was originally formulated as having a polymeric structure but whichhas been shown by X-ray crystallography to be the dimer (3) in which the nickel atoms aresandwiched between two r;3,?73-cot molecules (equation 12);88 see also ref. 1, p. 262. An analogouscomplex has been isolated from the reaction involving phenylcyclooctatetraene and here also anX-ray structural determination has confirmed the sandwich-like, dimeric structure.144 The ar-rangement of the cot molecules in these complexes should be compared with that observed in[(NiCO)3(cot)(CF3C=CCF3)] and discussed on p. 138.119

-4CH 2 =CH 2 I I

NiCl2 + 5^^^^> + 4AlEt3 • Ni—Ni + 4AlClEt2 + 3C5H10

do(2)

H

2[Ni(cdt)] + 4 cot ^ j ^ 2f—}| ^ N k | M I y ^ T N i N i (12^

I #' 11 / H C HH C C ye*

(3)

148 r]3-Allylnickel Complexes

A mixture of bis(r73-allyl)nickel complexes is formed on reacting allene with zerovalent nickel.Although the individual complexes have not been isolated, further reaction with phosphine orCO indicates that a mixture of (4) and (5) is present.12'68 A mixture of complexes is also formedon reacting [Ni(r;3,r73-Ci2Hi8)] with allene (equation 13). The nature of these species has been

• deduced from the structure of the coupling and insertion products formed upon reaction with COand alkyl isocyanide. For example, the isolation of the tetraenes (7) and (8) indicates that theinitial product of the reaction has structure (6).96'149

T Ni I Ni

(4) (5)

[Ni(7;V-Ci2H18)] + CH2=C=CH2 ^ T J ^

(6)

O J + 0 0 (i3)

(7) (8)

An unusual bis(?73-allyl) nickel complex has been isolated from the reaction of nickel acetyl-acetonate with diethylaluminium ethoxide in the presence of triphenylphosphabenzene (equation14) 183 A n X-ray diffraction study indicates that in the solid state the molecule has structure (9)while NMR studies suggest that in solution the allyl and alkene groups in the phosphorinyl ringexchange. (The crystal structure is shown on p. 151.) Related complexes have been prepared byreacting (9) with dimethylcyclopropene, alkynes, phosphines and triphenylphosphabenzene.

Ph

2Ni(acac)2 + 2 Et2AlOEt + 2 PQ^N^Ph + CH2=CH2 "2acacA1OEt>

Ph

Ph Ph

>£> >£>CH2 / Ph I CH2 / Ph||—Ni Ni ^ II—Ni- Ni (14)CH2 \ Ph I CH2 \ Ph

Ph Ph

(9)

37.6.2.2 Reactions

Chemical degradation is occasionally used to characterize bis(r/3-allyl)nickel complexes.Autocatalytic hydrogenation and pyrolysis normally proceed in a controlled manner to give a

773-Allylnickel Complexes 149

high yield of alkane or alkene, while treatment with inorganic acids results in the stepwise cleavageof the nickel-allyl bond; see, for example, refs. 45, 135. Photolysis of [Ni(773-*l-MeC3H4)2] givesa mixture of butene and coupling products,124 while reaction with CuCl2 leads to coupling.110

Reductive coupling followed by alkene elimination is also the main reaction observed on treatmentwith excess donor ligand and is occasionally accompanied (in the case of CO or isocyanide) byinsertion of a donor molecule. This aspect is discussed further in Section 37.6.5.

[Ni(773-C3H5)2] in DMF absorbs CO2 to give a 7-lactone, presumably through the intermediacyof the nickel carboxylate (10) (equation 15).129

[Ni(r/3-C3H5)2] + CO2 —• [Ni(OCOC3H5)(773-C3H5)] - ^ C^=O 05)

(10)

37.6.2.3 Structure and Bonding

NMR investigations indicate that the simple bis(?73-allyl)nickel complexes exist in solutionas a mixture of isomers. It is generally accepted that these differ in the mutual orientation of the7?3-allyl groups and any substituents present. For example, the four isomers (A-D) observed inthe NMR spectrum (Figure 1) of [Ni(r73-l,l-Me2C3H3)2] are assigned to the isomers (11)-(14).As expected, the spectra of [Ni(773-C3H5)2] and [Ni(r?3-2-MeC3H4)2] are compatible with thepresence of only two isomers and these are assigned to structures in which the allyl groups aremutually cis or trans.

1v fr fr f^ £ <r <r

(11) (12) (13) (14)

The only form detected in the solid state is the trans arrangement (see X-ray structural de-terminations below) and direct evidence for the cis arrangement is still lacking. Indirect evidencecomes from the observed geometry of the [Ni(PR3)(r/3-allyl)2] complexes discussed in the nextSection and from the analysis of the structure and composition of the product of the reaction of[Ni(7?3-C3H5)2] with diazomethane;62 a mixture of four hydrocarbons (15)-(18) is produced.Compound (15) is suggested to be the product of the reaction with the cis isomer and to resultfrom adduct formation followed by elimination (equation 16). The trans isomer, in contrast, issuggested to react by diazomethane-induced reductive elimination of hexadiene (16), which reactsfurther to (17) and (18) (equation 17). The ratio of (15) to the sum of (16), (17) and (18) is found

Ni + CH2N2 —* Ni -CH 2 N 2 rj-fT y C H 2 ( 1 6 )

< < <f(15)

^ <i« v. (17) (18)

150 rj3-Allylnickel Complexes

B

C

\

100 Hzi—i

D

3

5

\

B

rc

4) Ni

C

i

B

D

\

B

C

c2 c, C4 Solv/Cs

110 80 50 20 p. p.m.

H4 CH3(5)

A

B

X UJSL-JH,

fx8

p.p.m. 4 3 2 1

Figure 1 The 25 MHz ^C-fH} and 270 MHz lH NMR spectra135 of [Ni(773-l,l-Me2C3H3)2] in toluene-rf8at -20 °C

to correspond to the NMR spectroscopically determined relative concentrations of the two[Ni(if3-C3H5)2] isomers.

Samples of both [NiO73-C3H5)2] and [Ni(r/3-2-MeC3H4)2] rich in the trans isomer (6.5:1and 6.2:1, respectively) can be prepared by repeated recrystallization from pentane, whilepractically pure trans-[Ni(rj3-C3R5)2] can be obtained from the disproportionation of[(NiMe(?73-C3H5))2]. These samples equilibrate irreversibly at room temperature to give mixturescontaining 2.6:1 and 2.3:1 of the trans and cis isomers, respectively. The mechanism for thisprocess has still to be determined. Symmetry arguments backed by semi-empirical MO calculationsindicate that the trans arrangement (D2h) is energetically preferred to the cis arrangement (D2d)and that conversion by rotation about the metal-allyl axis is symmetry forbidden and hence ahigh-energy process.41

7]3-Allylnickel Complexes 151

The IR and Raman spectra of a number of [Ni(?73-allyl)2] complexes have been recentlypublished,27'55'58'99'133'135'152 while the inelastic neutron scattering spectrum of [Ni(773-C3H5)2]has been used to study the low-frequency (68-500 cm"1) metal-allyl vibrations.107 Detailed as-signments should be treated with caution since most frequencies in these systems are the resultof complex stretching and bending behavior. Most informative are the so-called C—C stretchingfrequencies, which occur around 1500 cm"1 and 1000 cm"1 and indicate the presence of a delo-calized double bond, and the metal-ligand stretching frequencies which fall in the range 300-400cm"1. In the case of [Ni(773-C3H5)2] the observation of only three metal-ligand absorptions isconsistent with a trans arrangement of the allyl groups.

The crystal structures of three simple bis(r;3-allyl)nickel complexes have been determined byX-ray methods, viz. (19),156 (20)135 and (21).52 In all three the allyl groups are mutually trans.The methyl group in the r/3-2-methylallyl complex is bent 12° out of the plane formed by the re-maining carbon atoms towards the nickel, an effect which is observed for other substituted ?73-allylnickel complexes. In addition, the structures of four binuclear complexes have been determined,viz. [{Ni(773,7?3-C8H8)}2] (3),88 [{Ni(r73,r?

3-PhC8H7)|2]144and(22)155and(23).183Thepentadienylgroup in (22) forms a three-centred bond to the nickel atoms which causes an increase in the doublebond character of the terminal C atoms. The allyl groups in the ethylene complex (23) adopt adistorted trans arrangement. Whether the 2.50 A separation of the nickel atoms in this moleculecorresponds to a chemical bond between these atoms is still to be decided. An X-ray structuraldetermination of the butyne complex corresponding to (23) indicates that here the nickel atomshave a non-bonding separation and that the r;3-allyl groups are mutually cis.183

1.49

198

126.9°

(19) (20)

(21)

1.99CH2

II—NiCH2

(23)

152 773 -A IlyInickel Complexes

The He(I) photoelectron spectra of a series of simple (?73-allyl)2nickel complexes have beenmeasured3'9'13'48-73'84 (see also ref. 1,-p. 322); that for [Ni(r73-C3H5)2] is shown in Figure 2. Anassignment is shown in Figure 3 in which the experimental results are compared with those ex-pected assuming Koopmans' theorem to be valid and those obtained using a semiempirical IN DOapproach. As can be seen, considerable discrepancy exists particularly for strongly localized or-bitals. The highest occupied MO is assigned to an orbital (7au) of purely ligand character andis followed by four MOs which are localized mainly on the metal. Other quantitive treatmentsof the bonding in this system are discussed in refs. 1, 40 and 123.

r6 7 8 9 10 II 12 13 14 15 16 17 18 19 20 cV

Figure 2 The He(I) photoelectron spectrum of [Ni(773-C3H5)2]84

IP(eV)A

1"

\2"

13--

14-- ¥r(a) (b) (c)

Figure 3 Comparison of the PE spectrum of [Ni(773-C3H5)2] (c) with the calculated ionization potentials assumingKoopmans' Theorem to be valid (a) and using the inverse Dyson equation (b)48

37.6.3 BIS(i73-ALLYL)NICKEL LIGAND COMPLEXES*

The bis(7/3-allyl)nickel complexes described in the preceding Section can react with donor li-gands either by addition to give 18-electron adducts, or by addition followed by rearrangementor displacement of the r;3-allyl groups. Adduct formation is generally observed on reaction withtertiary phosphines (equation 18).138 The crystal structure of the trimethylphosphine adduct (24)has been determined at low temperature: the two 773-allyl groups are mutually cis and are ap-


773 -A I ly I nickel Complexes 15 3

Table 2 [NiL(?73-Allyl)2] Complexes3

(18)

(24)

proximately parallel to each other even though the nickel atom has been drawn away from thecentre by the phosphine ligand. An NMR study indicates that the same structure is adopted atlow temperature ( < - 1 0 0 °C) in solution. At higher temperature equilibration of the syn andanti protons without dissociation of the Ni—P bond is observed, strongly indicating the inter-mediacy of an r/'-allyl species in this process. This is illustrated in equation (19) for one pair ofprotons. Phosphine dissociation occurs above —40 °C. An additional reaction which is observedin the case of the tricyclohexylphosphine adduct to [Ni(r73-C3H5)2] is reductive coupling of theallyl fragments to give the 1,5-hexadiene complex (25) (equation 20) which takes place above—20 °C. Syn ** anti equilibration is also observed if [Ni(r/3-allyl)2] complexes are treated withN-donors such as ammonia or pyridine without, however, it proving possible to isolate the inter-mediate adducts (see ref. 1, p. 342). The reaction of [Ni(r;3-l,l-Me2C3H3)2] with PMe3 isanomalous: instead of adduct formation, isomerization of one 773-allyl group into the 77'-form occurs(see Section 37.6.5).

rj3-Allyl Group L Ref.

C3H5 PMe3(24) 138PCy3 138PPh3 138duroquinone 11p-benzoquinone 1119,10-anthraquinone 111tetracyclone 111

l-MeC3H4 PMe3 138l-Pr iC3H4 PMe3 138l-PhC3H4 PMe3 1382-MeC3H4 PMe3 138

PEt3a 138

PCy3 138PPh3 138

l, l-Me2C3H3 PMe3 138PCy3 138PPh3 138

l,3-Me2C3H3 PMe3 138PEt3 138PCy3 138PPh3 138

cyclohexenyl PMe3 138cycloheptenyl PMe3 138cyclooctenyl PMe3 138i?3,i?3-C8Hi2 PPh3 26

P(OC6H4Ph-o)3 26,152,159rj\rj3-C9Hn PMe3 138

PPh3a 12

P(OPh)3 12P(OC6H4Ph-o)3

a 12i?3,i?3-C,2H,6 PPh3(27)a 12

Miscellaneous Complexes

[Nito3,iy3-C,2H,6)Ni(PPh3)2] (28) 12[Ni (7 ? V^ 3 -C , 2 H 1 8 ) ] (32)a 120, 135[Ni(i|2,i|3,i|3-C,sH24)] 74,135

a Earlier work is discussed and tabulated in ref. 1, pp. 342-345.

2.0681.407^v

[Ni^-CaHsk] + PMe3 —* U T N i I ^ P M e 3

154 r)3-Allylnickel Complexes

> H

Me3P' H2 H4 H5

Ni—PMe3

(19)

H4

Ni-PCy3

<

(20)

Other 18-electron adducts have been isolated from reactions involving allene and 1,3-dienes,although in these cases the parent bis(?73-allyl)nickel species have still to be isolated. The reactionof allene with zerovalent nickel complexes in the presence of phosphine occurs in a stepwise mannerand in addition to mono- and bis-allene nickel-phosphine species, the [Ni(PR3)(r73-allyl)2]complexes (26), (27) and (28) have been isolated (equation 21 ). ' '12 '138 The suggestion thatcomplexes of this type are involved in the nickel-catalyzed cyclooligomerization of allene is madecredible by the observation of ring closure upon treatment of these species with excess phosphine,CO or CS2. The crystal structure of (26) shows the carbon skeleton to be distorted: the allyl groupsare neither symmetrical nor equidistant from the metal atom while the o-methylene group isunusually short.150 An NMR study, however, indicates that, at least for the PMe3 adduct corre-sponding to (26), a symmetrical structure is adopted in solution.138

Idl

[Ni(cod)2] + PCy3 3 CH2=C=CH2- 2 cod

1.28

Ni—PPh3 (Ph3P)2Ni— fi —PPh3

(27) (28)

The product of the reaction of 1,3-dienes with phosphine-modified zerovalent nickel complexesis dependent upon the nature of the phosphine and diene: butadiene in the presence of trialkyl-phosphines reacts to give a [Ni(PR3)(r;

1,7;3-C8Hi2)] species which is discussed further in Section37.6.5. Analogous complexes are formed initially in the reaction involving triarylphosphines orphosphites, e.g. (29), but these rearrange irreversibly to give symmetrical [Ni(PR3)(r;

3,773-C8Hi2)]complexes, e.g. (30), which undergo spontaneous ring closure to give Ni(cod) species (Scheme1 )26,i52,i59 a n c j c a n hence be regarded as plausible precursors for the catalytic formation of cod.The 13C NMR spectra illustrating this process are shown in Figure 4. The structure of (30) isnot known with certainty (an X-ray structural determination is still lacking) but a detailed analysisof the NMR parameters suggests that, in contrast to earlier suggestions, the Cg chain is synsubstituted. Related [NiL(r/3,7;3-C8)] complexes have also been isolated from reactions involvingcis- and /ra«s-piperylene.153


[Ni(cod)2] P(OC6H4Ph-o)3- 2 cod

(o-PhC6H4O)3P

(29)

.Ni

P(OC6H4Ph-o)3

(30)

[NiP(OC6H4Ph-o)3(cod)] —•• ±[Ni(cod)2] + ^[Ni{P(OC6H4Ph-o)3)2]

Scheme 1

100 Hz

32 °C

L TBC4

BC3 C,

±o°c

* *JJUW*.

c2,c6

c3

Aw***W

\*

A A

*

solv.- 40 °C

AC8

yii& V^T^V

80 40 0 p.p.m.Figure 4 The rearrangement of [NiP(OC6H4Ph-o)3(T;3-C8H12)] (13C NMR, 25.2 MHz, toluene-^). The ab-sorptions labelled A, B, C and D are due to (29), (30), [Ni(cod)2] and [NiL2(cod)] respectively (* = pen-tane)159

Complexes having similar structures are probably formed in the reaction of the [NiL-(773-C8Hj2)] species discussed above with allene. Thus, the dark-red reaction mixture formedby treating [Ni(PPh3)(773,?73-C8Hi2)] with allene is suggested to contain a mixture of[Ni(PPh3)(7/3-allyl)2] complexes formed by the stepwise insertion of up to three allene moleculesinto the nickel-773-allyl bond. The initial product of this reaction, for example, is formulated as(31) (equation 22) on the basis of the structures of the C\ \ hydrocarbons liberated upon reactionwith CO or isocyanide.97

CH2=C=CH; CO,

(31) (22)

Ph3P

156 7]3 -A IlyInickel Complexes

A number of examples are known in which the donor ligand is an alkene. Of these the mostfamiliar is complex (32), which is formed in the reaction of zerovalent nickel with butadiene(equation 23).120 '135151 AnNMR study indicates that (32) consists of a mixture of two isomers,both of which contain ^//-substituted 773-allyl groups and a nickel complexed trans -alkene.Structures (32a) and (32b) are most consistent with the data and can formally be interconvertedby rotation of the complexed double bond.135 A related complex, which is also present as twoisomers, is formed in the reaction with isoprene135 (see also ref. 74).

[Ni(cdt)] + 3 ^ ^ v ^ —* [Ni(773,J73-C12H18)] + cdt (23)

(32)

(32a) (32b)

Complex (32) reacts with donor ligands with ring closure to give [NiL(cdt)] complexes. Adetailed NMR study of the reaction with PMe3 suggests that initially an adduct with the phosphineis formed in which one ?73-allyl group has been transformed into the 77'-form. Subsequently,isomerization of the anti -substituted r;3-allyl group occurs and is followed by ring closure to givea mixture of [Ni(PMe3)(W-cdt)] and (probably) [Ni(PMe3)(/,/,c-cdt)].138

Unstable adducts with alkenes have also been reported to be formed upon reaction of [Ni-(T7 3-C 3H 5)2] with duroquinone or tetracyclone.1 •'*l !-125

37.6.4 [(NiX(773-ALLYL))2] COMPLEXES*


Oxidative addition of an allyl derivative to a zerovalent nickel complex is probably the mostconvenient method for preparing the [{NiX(773-allyl)}2] complexes. Nickel tetracarbonyl wasformerly the reagent of choice and still finds some application (equation 24),32'53'96'137 althoughit has largely been displaced by bis(cyclooctadiene)nickel (equation 25).52,83,90,I45,146 R e i a t edto these is the reaction of an allyl halide with nickel vapour or the active nickel powder formedby reducing nickel chloride with potassium.127

OMe

2[Ni(CO)4] + 2 ^ s ^ B r -+ [|NiBr(773-2-MeOC3H4))2] + 8CO (24)

CH2Br

"~^ ' + 4 cod (25)

Controlled protonolysis of bis(?73-allyl)nickel complexes is occasionally re-ported5- 14,45,117,118,145,148 a n c j has been used, for example, to prepare the thiol derivative (33)(equation 26) and the triketenoate and anthraquinone derivatives (34) and (35). A similar reactioninvolving the trithiapentalene (36) leads to the heptatrithionediol derivative (37) whose structurehas been established by X-ray methods (equation 27).118 If this reaction is carried out in thepresence of excess [Ni(773-C3H5)2], the cluster compound (38) is formed. The prismatic ar-rangement of the nickel atoms with face-bridging sulphur atoms has been confirmed by X-raycrystallography.115


2[Ni(773-2-MeC3H4)2]


2H2S —> [{NiSH(773-2-MeC3H4)}2] + 2C4H8 (26)

(33)

2[Ni< S S ~C6HioXXX(36)

i 117.9°(27)

(37)

(38)

Ni-Ni(trigonal base), 2.79-2.85; Ni—Ni(quadratic side), 2.62-2.69; Ni—S, 2.33-2.60, Ni2—C4, 2.05(1);Ni2—C5, 1.99(2); Ni2—C6, 2.05(2); C4—C5, 1.42(3); C5—C6, 1.36(3) A; ZC4C5C6, 119(2)°

It is appropriate to mention here that supported nickel catalysts may be prepared by reacting7;3-allylnickel complexes with alumina or silica5 ] ,54,60,66,85,112,126 o r a styrene-difluorobutenoicacid copolymer.186 The initial step is presumably protonolysis of an 773-allyl group or cod molecule(equations 28, 29).

[Ni(T,3-C3H5)2] —Si—OHI

'—Ni—O—Si— + C3H6 (28)

[Ni(cod)2] + polystyrene—CF2CO2H

NiOCOCF2 polystyrene

+ cod (29)

Anion substitution has been reported for reactions involving organomagnesium or organolithiumreagents (equation 30) 1 3 6 as well as inorganic salts (equations 31, 32 ) . 1 1 7 1 4 5

[(NiBr(7rM,3-Me2C3H3)j2] + 2MeMgBr

[{NiBr(7?3-2-MeC3H4)}2] + 2LiNMe2

[jNiMe(r73-l,3-Me2C3H3)2(]

[{NiNMe2(r?3-2-MeC3H4)S2] + 2LiBr (31)

2MgBr2

(30)


[|NiBrO73-C3H5)j2] + 2TlBr (32)

A number of examples are known in which a complexed alkene is converted into an r;3-allylgroup. Thus, bis(cyclooctadiene)nickel reacts with acids to give, in some cases, ?73-cyclooctenyl-nickel species (equation 33). This reaction probably proceeds through the intermediacy of an77''2'5-cyclooctenylnickel complex which in the case where X is acetylacetonate or acetate has beenisolated and shown to undergo the expected thermal rearrangement (see ref. 1, p. 350, and ref.166). Reactions involving thiols proceed directly to the 7/3-cyclooctenyl complex. Related is thereaction of tetramethylcyclobutadienenickel dichloride with methylmagnesium chloride in whichthe ?73-cyclobutenyl species (39) is generated (equation 34).167

2[Ni(cod)2] 2HX - 2 cod

|Q[-NiCl2)\ /2

2 MeMgCl

NiX(33)

2MgCl2 (34)

(39)

Some [{NiX(?73-allyl))2] complexes (notably the iodide and trifluoroacetate) are active catalystsfor the polymerization of 1,3-dienes. Careful NMR studies8'16'17'35'44-57'63'103'113'122'130 (see alsoref. 165, p. 225) indicate that this reaction proceeds by diene insertion into the nickel-carbon bondto give a new ?73-allyl species whose configuration (syn or anti) controls the structure of the re-sulting polymer {trans- or m-l,4-polydiene). This is illustrated in equation (35) for the reactionof ?73-perdeuterocrotylnickel iodide with 2,3-dimethylbutadiene, but has also been investigatedfor reactions involving butadiene and other dienes. What is presumably an insertion reaction hasalso been observed upon treatment of nickel chloride and zinc with butadiene in acetonitrile(equation 36).63 Water is believed to be the source of hydrogen in this reaction and in the caseof isoprene an intermediate ionic species (40) has been isolated. An insertion reaction also occurson treating 773,?73-octadienediylnickel triphenylphosphine with the diethyl ester of acetylenedi-carboxylic acid (equation 3.7).26 What may be a related complex is formed on reacting bis(cy-clooctadiene)nickel with butadiene and/?-C6H4CH=NPh, although the formation of a simpleheteroalkene nickel complex has not been excluded;95 see also ref. 191.

C4D7CH2-CH2C4D7 V -

(f—Nil + -0—Nil (35)

(65%) (35%)

2NiCl 2Zn 4MeCN

(40)

EtOH ( < r N i C l l 2ZnCl2 + 4MeCN (36)

9Ph3P-N

4EtO2CC=CCO2Et

-PPhj EtO2C

EtO2C

(37)

ri3-Allylnickel Complexes

Table 3 [{NiX(?j3-Allyl)}2] Complexes

159

rj3-Ally I group X Ref.

C3H5 Cla 23 ,45 ,61 ,70 ,91 ,99 ,110, 164, 189

Bra 22,70,99, 107, 164,189

Ia 15,70,99,164, 189NMe2 145OMea 145SH 148SMe(46) 145SEt 145OCOMea 42,43OCOCCl3

a 5OCOCF3(49)a 5, 17,43,146OSO2C6H4Me 5Mea 136Et 136CHCH2CH2

a 136Pha 136mesityla 136triketonate (32)RI = R4 = C o 2 E t , R2 = R3 = H 117triketonate (34)RI = R4 = GO2Et, R2—R3 = —(CH2)2— 1178-hydroxyanthraquinone (35) 117

l-MeC3H4 Cla 17 ,18 ,22 ,45 ,49 ,61 ,62,98,110,124

Bra 83Ia 17,62OCOCF3

a 17MgMe2Cl(ether)a 136Mea 136

2-MeC3H4 Bra 53,127NMe 2 145OMe(45) 145SH (33) 148SMe 145OCOCF3

a 17Mea 136

2-Me3SiC3H4 Cl 822-MeOC3H4 Br 322-EtOCOC3H4 Br (44)a 532-PhC3H4 Br 145

NMe2 145OMe 145SMe 145

2-BrC3H4 Br 145NMe2 145

l, l-Me2C3H3 Cl 49,63,124Bra 53,137

l,l-Me,C1 6H3 0C3H3 Br 137l,l-Me,C4 1H6 7C3H3 Br 137(+)-pinenyl Cl 52, 140

Bra 52, 140I 52, 140

(-)-pinenyl Br 521,3-Me2C3H3 Cla 18,22,29,49,87, 124,

130I 22, 49, 87OCOCC13 49OCOCF3 49OSO2C6H4Me 49SMe 145Me(47)a 109, 128, 136MeAlMe3(43) 136

cyclopentenyl-Br2 CdBr 121cyclohexenyl Cla 18,49cyclooctenyl Bra 166

acaca 166SEta 166

160 V3 -A I ly I nickel Complexes

Table 3 (continued)

a Earlier work is discussed and tabulated in ref. 1, pp. 345-354, 376-393. b See p. 89.

37.6.4.2 Reactions

37.6.4.2.1 In which the rj 3-aIlylgroup is displaced

Hydrogenation61'130 or protonation5'45'130 occur with cleavage of the metal-allyl bond (equation38). The thiol complex (41) undergoes intramolecular protonation at room temperature (equation39) J48 while oxidation with cupric chloride liberates an allyl chloride.110

[|NiBr(j73-C3H5)!2] + 2HBr —* 2NiBr2 + 2CH2=CHMe (38)

[{NiSH(?3-C3H5))2] —• 2NiS + 2CH2=CHMe (39)

(41)

Reaction with organic halides leads to coupling of the organic groups. An example is shownin equation (40). This and a number of related reactions, e.g. the formation of allylic alcoholsupon treatment with ketones, are of some significance in organic synthesis and are discussed indetail in Volume 8.

—C16H33\r N i B r IOAc OAc

-2NiBr2

(40)C15H31

OAc

The thermal decomposition of the [{NiX(r73-allyl)}2] complexes is seldom a clean reaction andin general a mixture of monoalkene coupling products and 1,3-diene is formed. For example,[jNiCl(773-l-MeC3H4)}2] decomposes in xylene at 140 °C to give a mixture of butenes (23.5%),octadiene (23%) and butadiene (5.5%).18-148 A similar mixture of products is obtained on pho-tolysis.37'124

An unusual reaction is that of [fNiBr(773-C3H5))2] with nitric oxide at low temperature (equation41); NO is inserted into the syn-C—H bond to give (42) in which an a,/3-unsaturated oxime iscomplexed to nickel.169 At room temperature a polynuclear nitrosyl nickel bromide [)NiBr(NO)jrt]is formed.

[{NiBr(»;3-C3H5)j2] + 4NO — 2[NiBr(NO)(CH2=CHCH=NOH)] (41)

(42)

Reaction with donor ligands is discussed in Section 37.6.5.

r/3AllyI group X Ref.

SPh 166Mea 136

l,l,3,3-Ph4C3H Br 14

Miscellaneous Complexes[{Ni(7?3-C3H5)}6S3] (38) 115[{Ni(773-C3H5)j2(triketonate)]Ri = R 4 = Me, R2 = R3 = H 117RI = R4 = cO2Et, R2 = R3 = H 117Ri = R4 = C o 2 E t , R2 = R3 = —(CH 2) 2— 117{Ni(^3-C3H5)}2(anthraquinone)] 117{Ni(773-C3H5)}2(heptatrithionediate)] (37) 118Ni(r;3-1 -C5H8C2(CO2Et)2C3H4)] 26, 152(NiCO)4(C3Cl4)2] (48) 94, 105(^Ph4C4)NiC3Ph3Ni(77-Ph5C5)]b 89

rf3-Allylnickel Complexes 161

37,6.4.2.2 In which the allyl group remains intact

The [jNiR(773-allyl)J2] complexes may be prepared by reacting a halide precursor with an or-ganolithium or organomagnesium reagent (equation 42).136 Treatment of [(NiMe(r;3-l,3-Me2C3H3)J2] and related complexes with the Lewis acids AlMe3 and MeMgCl results in mo-nomerization and formation of bimetallic species, e.g. (43). Presumably related to this reactionis that of [Ni(?73-C3H5)2] with TiCU in which, it has been suggested, an allyl group is initiallytransferred from nickel to titanium to give [ N i C K T i C ^ H s X ^ ^ H s ) ] 2 1 ' 3 4 ' 1 1 3 (see ref. 1, p.351).

;—NiBr 2 MeMgCl-2MgBrCl

(J—NiMe

2AlMe3

(42)

(43)

Reaction with acceptor molecules such as chloranil or trifluoroacetic acid results in the formationof charge transfer complexes which have been shown to be active catalysts for the polymerizationof butadiene. The composition and nature of these species is not clear and reaction is generallyaccompanied by at least partial displacement of the allyl groups29'44'132 (see ref. 1, p. 351).

The disproportionation of [jNiX(r/3-allyl)}2] complexes to give bis(r;3-allyl)nickel systems hasbeen discussed in Section 37.5.2.

CO2Et

Me

CO2Et

(44) (45)

1.982

1.411

2.015

1.959

2.040

(47)


The [(NiX(i73-ally!)!2] complexes are in general dimeric. Spectroscopic investigations indicatethat they exist in solution as mixtures of isomers. For example, [jNiMe(r/3-C3H5))2],[|NiBr(773-(+)-pinenyl)}2] and [|NiOMe(773-2-MeC3H4)J2] adopt two forms in solution,[!NiSH(773-C3H5)J2] exists in three forms and [(NiN(Me)Ph(773-C3H5)!2] in no less than five.The four available X-ray determinations (44),163 (45),145'178 (46)145'178 and (47)109<178 indicatesome of the possibilities: the allyl groups or substituents on the group X can adopt a cis or transarrangement while the 1^2X2 units can be planar or puckered. The allyl group itself experiencestwo main distortions: (i) substituents lie in the allyl plane (44) or are bent towards the nickel (45,47), and (ii) the dihedral angle (yp) between the allyl and N12X2 planes increases to a value greaterthan 90° [for (44) yp = 106°].


MO considerations indicate that in the case of the methoxy complex (45) a structure havinga planar Ni2<I)2 moiety is energetically favoured whereas in the case of the thiomethyl complex(46) both puckered and planar arrangements are of similar energy.178'179 Preliminary electrondensity determinations come to the surprising conclusion that there is no direct metal-metal bondin either the methyl or methoxy complex (45) and (47), whereas in the thiomethyl complex (46)there is a weak interaction.178 Clearly the bonding situation in the [{NiX(773-allyl)}2] system ismore complex than previously supposed and further theoretical and structural work will be nec-essary before a satisfactory account of the bonding can be given.

A complex having the stoichiometry [ ( N i C O ^ C s C l ^ ] and the unusual structure (48) isformed on reacting tetrachlorocyclopropene with nickel tetracarbonyl. The molecule containsa planar N i ^ b ring with two ring-opened C3CI3 fragments bridging the two pairs of nickelatoms.94'105 The bonding situation in (48) is reminiscent of that found in [(?7-Pri4C4)Ni(C3Ph3)-Ni^-PhsCs)], which is one of the products of the reaction of nickel bromide with the diethyletherate of pentaphenylaluminacyclopentadiene and has been shown by X-ray crystallographyalso to contain a bridging C3 group (see p. 89).89 In this case, however, the central C atom of theC3 unit interacts with the nickel atom bonded to the 77-cyclobutadiene moiety and as a result thisNi—C bond distance is significantly shorter (2.11 A) than that observed in (48) (2.44 A).

o o

The dynamic behaviour of [|NiOCOCF3(r;3-C3H5)J2] in solution has been investigated by NMR

spectroscopy. The results indicate that two species (49) are present which interconvert by openingof the [NiOC(CF3)O]2 ring and not by the more familiar rj3 -++ rj1 exchange (equation 43).Compound (49) is an active catalyst for the polymerization of butadiene and in the presence ofsuitable solvents equibinary 1,4-polybutadiene is formed. The cis: trans ratio in the polymer chainis suggested to be controlled by the conformation (single-els' or single-trans) of the coordinatedbutadiene molecules and not by the geometry (syn or anti) of the intermediate ?73-allyl group.146'168

!o (43)

Niv Ni Ni/\

o

CF3

(49)

The IR and Raman spectra of various [|NiX(773-allyl)j2] complexes have been repeatedlymeasured and detailed assignments have been used to calculate force constantdata.22'23-27'42'43'70'87'98'99-133 Inelastic neutron scattering107 has been used to obtain spectroscopicdata for [|NiBr(773-C3H5)}2] down to 25 cm"1. Characteristic are absorptions around 1500, 1000and 500 cm"1, which are attributed to *>ccc(A"), PCCC(A') and <5Ccc(A') respectively, as wellat ca. 400 cm"1 (*>Ni—c) and ca. 250 cm"1 (i/Nj__Hai).

A CNDO MO calculation for [{NiX(i73-C3H5)}2] where X = Cl or I, has been carried out.123

The calculations indicate that the electronic distribution in the allyl groups is similar to that infree [ ^ H s ] " while the different electronegativity of the halides is reflected in the charge on thenickel atom: +0.42 for the iodide and +0.30 for the chloride.

773 -A IlyInickel Complexes 16 3

37.6.5 [NiX(L)(r?3-ALLYL)] COMPLEXES*


Monomerization of the dimeric [NiX(?73-allyl)] complexes by reaction with a donor ligandis the most convenient method for preparing adducts (equations 44, 45).32,52,64,83,136 Althoughthe reaction with P-donor ligands is by far the most common, examples involving bicycloheptene30

or dibutyl sulphide64 have also been reported.

Rr

(MeO—(— NiBr) + 2PPh3 —» 2 MeO—(—Ni^ (44)

v \ h \ \p p h 3

A \ > /Me( a—NiMe I + 2PPhPr1

2 —* 2C—Ni^ (45)

V A / ?pm'2

The enthalpy of the reaction of [|NiMe(?73-l,3-Me2C3H3))2] with tertiary phosphines andphosphites has been measured calorimetrically and an attempt has been made to correlate theresults with the electronic and steric characteristics of the ligand as defined by Tolman170 (seep. 25). A regression analysis of the results suggest that both properties are of comparable im-portance. However, those for reactions involving ligands containing phenyl or benzyl groups areanomalous.128

A second important preparative method is the oxidative addition of an allyl derivative to azerovalent nickel species (equations 46-48).67 '72 '86 '131

OPh / ^ O P h

[Ni(cod)2] + PPh3 + S ^ / —+ <f-Nif + 2 cod (46)% ^ P P h 3

[Ni(CO)4] + MeCO2CH=C(Me)CH2Br + lutidine

MeO2C

—• — a — N i ^ + 4 C O (47)

q\ Cl

^ - N i ^ + CH2=CH2 (48)PPh3

A number of reactions involving insertion of CO2, SO2 or phenyl isocyanate into a Ni—C bondhave also been reported (equations 49-51).108 '139 '173 The product of the reactions with SO2 areS-sulphinato complexes while the initial product of the reaction with phenyl isocyanate is thenickelaiminoester (50) which rearranges at room temperature to the nickelaanilide (51). Anunusual elimination reaction is observed on treating the nickel alkyl complex (52) with HC1:norbornene is eliminated to give the r;3-allyl nickel species (53) (equation 52). This process canbe reversed by treatment with potassium acetate.30

^ ( r N i ~ ) " + PMe3 + c ° 2 —* ~ { r N i / ^ ^ (49)

PMe3

O2

/ - N i - \ + PCy3 + SO2 —• V-Ni^f ^ (50)N >f ^ ^ P C y 3



Cy3

Ni J + PhNCO

Cy3PPh

(50) (51)

NiOCOMe

(52) (53)

(51)

(52)

Selective protonolysis of the Ni—C (equations 53-55)136-139-152 or Ni—N bond (equation 56)139

has attracted some attention.

(50) + MeOH/HCl NHPh (56)

Other synthetic procedures of lesser importance involve allyl or alkyl Grignard reagents(equations 57, 58)!'65 (the reaction of the sodium salt of diallylisocyanurate with nickel chloride104

is perhaps related), displacement of a ligand molecule from the cationic [NiL2(?73-allyl)]+ species(equation 59)63 (this might be mechanistically related to the reaction of [Ni(PPli3)4] with HC1and butadiene which has been recommended102 as a method for preparing [NiCl(PPh3)-(r/3-C4H7)]) and the bromination of the cyclopentadienyl ring which has been reported for oneexotic case (equation 60).121

MeMgCl

[NiCl(C6Cl5)(PMe2Ph)2]

'_Ni(PPh3)2+ZnCl3 2py

- [NiMe(PPh3)(*?3-C3H5)] + MgBrCl (57)

^C 6 C1 5

^ ^PMe 2Ph

XI- P P h 3 .

MgBrCl (58)

+ py2ZnCl2 (59)

BrBr

Br

PPh3

»—Ni:Br

"CdBr(60)

<?-Ni^ + HBr —• € — N i C + C H 4 (53)X X P P h 3 > ^ P P h 3

Ai-PC^ + < ^ C O > H - ^ ^ _ N - O Y ^ ^ + C3H6 (54)

^ ^ PC^

Ph3P—Ni + HC1 —^ Ni (55)^ ' / \

Ph3P Cl

[NiBKPPh3)fe3-C3H5)]


Table 4 [NiX(L)(r?3-Allyl)] Complexes3

tf-Allyl X L Ref.

C3H5 Cl PMe(Et)menthyl 143PMeCBu^menthyl (62) 143PMe(Cy)menthyl 143PMe(Bul)Ph 143CNBu1 72

Br PPh3a 136

I SBu2 64SH PMe3 148SO2C3H5 PMe3 173

PCy3 173OPh PPh3

a 131OCOC3H5 PCy3 139Me t>Ph3 136C6C15 PMe2Ph 65

l-MeC3H4 Cl PPh3 63, 102, 124Br PCy3 83Me PCy3

a 83,136C6C15 PMe2Ph 65

2-MeC3H4 Cl C7H8a 30

PPh3a 30,37

SO2C4H7 PMe3 173PCy3 173

OCOC3H5 PCy3 139OCOC4H7 PMe3 108,139

PCy3 108,139C6C15 PMe2Ph 65

2-MeOC3H4 Br PPh3 32l , l -Me2C3H3 Cl PMeCPrOmenthyl 143

PMe(But)menthyl 143PPh3 63

CH 2 CH=CMe 2 PMe3 (54) 138l,l-Me,CCl3CH2C3H3 Cl P(OPh)3 2l,2-Me2C3H3 Cl PPh3 63l,2-Me,MeCO2C3H3 Br C7H9N (65) 67(+)-pinenyl Cl PPr^Bu^Ph 140

Br PMe(But)Ph (66) 81,140PPr^Bu^Ph 140PMe(Prj)Ph 140PMe(But)Ph 140PMe(Pr!)Cy 140PMe(Pr)Ph 140

Br PMe(Pri)But 140PMe(But)menthyl 143PPh3 52

C6H5CH2 Cl PPh3 86l,3-Me2C3H3 Cl chloranil3 29,44

Me P(Prj)2Ph (67)a 20,136P(menthyl)2Me (68)a 20

Br CdBr 121l,2,2-Me3C3H2 Cl PPh3 63l,l,3-Me2,CO2MeC3H Br NCMe (69) 19l,l,3,3-Ph4C3H Br PEt3 14

PPh3 14

Miscellaneous ComplexesNiCl(PPh3)(773-l-C5H9C3H4)] 152NiPh(T71,773-l-C5H8C3H4)][Li(TMEDA)2] (58) 141Ni(PCy2)(77',7/3-l-C5H8C3H4)2][Li(THF)4] (57) 142Ni(PCy3)(r71,7?

3-l-C5H8C3H4)]a 80, 138, 152Ni(PCy3)(771,7?

3-l-C7H12C3H4)] (73) 152Ni(PCy3)(r?

1,7?3-l,l-Me,C6H10C3H3)] (55) 153

Ni(PCy3)(7;l,773-l,2-C6H1o,MeC3H3)] (70)a 152Ni(PCy3)(r/ l,r/3-l,l,2-Me,C7Hi2,MeC3H2)] 152, 176Ni(PCy3)(T/3-l-C5H8C(==NPh)OC3H4)] (50) 139Ni(PCy3)(773-l-C5H8C(O)N(Ph)C3H4)] (51) 139

[NiOMe(PCy3)(773-l-C5H8CON(Ph)HC3H4)] 139[Ni(PPh3)(773-l-C5H8C(=NPh)OC3H4)] 139[Ni(PPh3)(773-l-C5H8C(O)N(Ph)C3H4)] 139[|Ni(PPh3)(i?

3-1 -C5H8CO2C3H4)}2] (74) 139

166 ri^-Allylnickel Complexes

Table 4 (continued)

a Earlier work is tabulated and discussed in ref. 1, p. 360.

An unusual reaction is observed on treating l-ethyl-2,4,6-triphenylphosphorinyllithium withnickel chloride (equation 61);183 an X-ray structural determination (see p. 171) of the productindicates that the phosphorinyl group is acting as a P-donor to one nickel atom and as an r;3-allylligand to a second.

2NiCl- (61)

The observation that [NiCl(PCy3)(773-C3H5)] forms an adduct with AlCl2Me (equation 62)suggests a possible role for Lewis acids in catalysis.174 What are probably related complexes havebeen isolated from reactions of [|NiX(773-C3H5)}2] with phosphines and TiCl4, A1C13 or Ni-(OCOCC13)2.21'116'188

A few examples have been reported in which the treatment of a bis(r?3-allyl)nickel complexwith a donor ligand results in the conversion of one r;3-allyl group into the rj'-allyl form (equation63).138 The NMR spectrum of (54) indicates that fast r;3 ++ 77! exchange is occurring even at - 9 5°C. Presumably steric interaction between the anti-Me group and the ligand destablizes the ex-pected 18-electron adduct. Spectroscopic evidence indicates that a related system is formed initiallyon the reaction of [Ni(r73,?73-Ci2Hi8)] with trimethylphosphine and that this then reacts furtherto give [Ni(PMe3)(cdt)].138 The intermediate formation of species related to (54) have beenproposed to account for the observed equilibration of the syn and anti protons in a number of[NiL(r73-allyl)2] complexes and on treatment of bis(?73-allyl)nickel with N-donors.1138

Structurally related to (54) are the complexes formed on treating phosphine-modified zerovalentnickel complexes with 1,3-dienes. In the case of butadiene, NMR investigations have shown thatthe initial product is a [NiL(V,773-C8Hi2)] species which, where L is a triarylphosphine or phos-phite (but not a trialkylphosphine), rearranges further to a symmetrical [NiL(r73,r;3-C8Hi2)]complex (see Scheme 1, p. 155).159 The initial product of the analogous reaction involving isopreneis a [NiL(77l,i;3-CioHi6)] species (55) in which the methyl groups are bonded to C-3 and C-6(equation 64). This complex rearranges to give a mixture of isomers having 2,6 and 2,7 substitution.

T/3- Ally I X L Ref.

[{Ni(PCy3)(T;3-l,2-C6H1oC02,MeC3H3)}2] (64) 108, 139{Ni(PMe3)(T7-1,2-C6H 10CO2,MeC3H3)h] 139{Ni(PPh3)(r/

3-1,2-C6H 10CO2,MeC3H3)}2] 139{Ni(PMe3)(T/3-l-C9H14CO2C3H4)h] 108, 139Ni(PCy3)(7?

3-l-SO2C5H8C3H4)] 173Ni(PCy3)(773-l,l-Me,S02C6HioC3H3)] (72) 173

[{NiCl(iy3-Ph3C5H5PEt}2] (71) 183

2

/ - N i ^ + AlCl2Me — • / - N i ^ ^AlCl2Me ( 6 2 )X^ ^ P C y 3

XN ^ P C y 3

>T N i A + PMe3 _ h < ^ — ^ ^ N ^ (63)

(54)

r]3-Allylnickel Complexes 167

Similar species have been isolated from reactions involving piperylene and 2,3-dimethylbutadieneand in the reaction of bis(r;4-2,3-dimethylbutadiene)nickel with tricyclohexylphosphine (equation65).176

[NiL(cdt)] + 2

(55) (64)

PCy3 — ^Ni ' 1 (65)

Further examples of [NiL(rj* 9ri3-C%)] species have been isolated from reactions involving anionicnickel complexes. The phosphide (56) reacts with butadiene to give the binuclear species (57)(equation 66),142 while the reaction of divinylcyclobutane with the anion formed by treating[Ni(cdt)] with phenyllithium in TMEDA leads to a complex (58) in which the phenyl anion isacting as a donor ligand (equation 67).141 A binuclear complex containing a Cg chain, viz. (59),has also been isolated from the reaction of butadiene with a nickel methyl species (equation 68).175

(56)

-4CH2=CH2

(66)P'~Cy2

(57)

[NiPh(cdt)]-Li(TMEDA)2+ + Q ^ ^ ^ ^ 'Ai J Li(TMEDA)2

+ (67)

+ 2 ^ ^ -TZT- * ^ ^ ^ r m

(59)

37.6.5.2 Reactions

37.6.5.2.1 In which the rj 3-allylgroup is displaced

The reactions discussed here have been used in general to obtain structural information on thecomplexes involved. The reaction with excess ligand presumably proceeds through the intermediacyof [NiXLw(?73-allyl)] complexes and these are discussed further in Section 37.6.6.

Treatment of the 773-allylnickel alkyl species with excess ligand frequently results in couplingof the organic groups (equations 69, 70).26'80'136>141-152 Related reactions involve the bis-(?73-allyl)nickel species described in Section 37.6.2 and in some cases the intermediate alkeneor ^-allylnickel species has been isolated.135-138'139 The reaction is not confined to CO or phos-

[|Ni(CH2=CH2)2l2PCy2] Li(THF)/ + 4 ^ \ ^

[Ni(^r)J


phines and that with alkenes has been propagated as a method for preparing nickel alkene com-plexes (equation 71 ).125 The reaction with CO or isocyanide is sometimes accompanied by insertion(equations 72, 73).68,96,97,i 35,149 Some of these insertion reactions are of synthetic interest andare discussed further in Volume 8.

Coupling is also observed on reacting 773-allylnickel S-sulphinates and carboxylates,139 ther;3-allylnickel triketonoate (60)117 and the cluster compound (38)115 with CO (equations 74-77).Diallyl sulphide is also the product of the reaction of nNiSH(773-C3H5)}2] with CO.148

( / - N i M e ) + 8 CO —> 2 ^ ^ ^ + 2[Ni(CO)4] (69)

N i J + 3 CO —+ ^ { ^ ) + [Ni(CO)3(PCy3)] (70)

[Ni(?;3-C3H5)2] + 2 cod —• [Ni(cod)2] + j ^ s ^ ^ (71)

I J [ X 1 + 5CO — f I 1 1 + [Ni(CO)4] (72)

Ph3p-.iiii \ ^ ^ c d (?3)

^T^ oN i ^ y ^ s + 3 C ° " ^ ^ ^ v / S ^ ^ . + [Ni(CO)3(PMe3)] (74)

Me3P S^

C y 3 p / N i ^ O ^ ^ + 3 C O ~ ^ ^ ^ ° Y ^ f + [Ni(CO)3(PCy3)] (75)

?' ^ "? + 8CO "^ ° ° ° + 2[N i(C°)4] (76)

(60)

[{Ni(773-C3H5)|6S3] + 24 CO —* 3 ^ ^ ^ S ^ ^ V + 6[Ni(CO)4] (77)

(38)

- Ally Inickel Complexes 169

In a few cases (equations 78, 79),92'171 the allyl group reacts with the phosphine to give aphosphonium salt.

I

;— Ni— CO + 2 CO

PPh3

+ [Ni(CO)3(PPh3)] (78)

— Ni+(PBu3)2 C1OP h

3PBu3 [Ni(PBu3)4] (79)

Other modes of reaction include hydrogen transfer from the allyl group to the anion (equation80),145 while homolytic displacement of the tetraphenylallyl radical is observed on reaction of[Ni(773-l,l,3,3-Ph4C3H)2] with CO.14 A related reaction is that of phosphines with the[ N i L ^ - C g H ^ ) ] species discussed on p. 154 in which cleavage of the Cg chain occurs and bu-tadiene is eliminated (equation 81).152

(/£_NiOMe)2 8PEt2Ph 2 MeOH 2[Ni(PEt2Ph)4] (80)

Ph3P— 3PPh3 [Ni(PPh3)4] (81)

Additional reactions which have been used to characterize [NiXLn(773-allyl)] species includeprotonolysis and hydrogenolysis. The course of the reaction with acids depends upon the natureof the nickel complex: neutral species react with protonolysis of the ?73-allyl group while the cationicr/3-crotyl complex (61) has been shown to react with morpholine to give l-(./V-morpholino)-2-butene (equation 82).36'190 This last reaction probably has mechanistic relevance to the catalytictelomerization of morpholine with butadiene. Hydrogenolysis can be carried out either auto-catalytically or in the presence of catalytic amounts of palladium or bis(cyclooctadiene)nickel.The photolytic decomposition of [NiCl(PPh3)(773-l-MeC3H4)] has also been investigated.37'124

P(OEt)3

PF HN p •— N 0

(61)

[NiH|P(OEt)3)2]+PF6-

(82)


Complete crystal structure determinations have been published for 11 [NiX(L)(?73-allyl)]complexes (62)-(72). In addition, partial determinations have confirmed the structures of (73),152

(74)139 and (75).! '74 The nickel atom in these complexes occupies an essentially square planarenvironment. A trans effect is frequently observed: the Ni—C bond trans to X is shorter thanthe cis Ni—C bond while the associated C—C bond is longer. This reflects a partial localizationof the 7r-electrons in the allyl group. A MO calculation for [NiCl(PMe3)(773-C3Hs)] also indicatesa significant trans effect.181 Distortions in the allyl group result in a tilt of substituents towardsthe nickel atom and in the generation of a dihedral angle between the molecular and allyl planesof ca. 110-120°. In addition, a 5-10° in-plane twist of the allyl group has been noted for the?73-allylnickel alkyl complexes.

170 r}3-Allylnickel Complexes

1.99

Me\

HC

HC CH2

Me

(62)143

—Ni <~H2

/ C 1

CH

CH2 H2C

TJ

(63) 175

.PPr'a

Cy3P

.Me 1.38^40

H2

'Me

(64)10*

Me

4'•495XCH2^07 /1.444/ Xl.965

1.989pV N ' 97 2°eT456i X 3 2 9

CH2 Br2.008

(65)67

Me MeN C

Bu

1.98

H

H106

:y Me

(67)20

(66)81

M e ^

2.103

menthyl -

Me

1.999H

1.443 ( ^1 408 M e

H 1 H M62

P ^ ^ M ementhyl

(68)20

H

c

I24l\/'3

Me

X C

(69)19

^Mei.88/NCMe

99^9°

•32>Br

. rj3-Allylnickel Complexes 171

Et

H Ph2.001

2,040

Ni-PCy3

CH2

Me

(73)

1.93-2.08

Ni—PPh3 Ni2.225/ \2253 AlCl2Me

Cy3P C l ^

(75)

The [NiX(L)(r/3-allyl)] complexes are chiral and therefore exist as enantiomers (see p. 83).If the ligand is also chiral, two pairs of diastereoisomers result which can in principle be separatedby crystallization. The existence in solution of diastereomers was first confirmed for complexesformed by [|NiMe(773-l,3-Me2C3H3))2] with optically active or prochiral ligands, e.g. (76) and(77),I72 and forms the basis of a useful method for separating optically active phosphines:140143

the adduct to various [{NiX(773-allyl)}2] complexes are separated by crystallization and the opticallypure phosphine is then released by exchange with trimethylphosphine. This method has been usedto separate both Horner phosphines, e.g. PMe(Bul)Ph, as well as phosphines in which the opticallyactive centres are both at phosphorus and in the substituents, e.g. PMe(But)menthyl. The absolute

172 3 -A llylnickel Complexes

configuration of the phosphine for the two examples mentioned above have been confirmed bycrystal structure determination of their nickel adducts (62) and (66).

)V—Ni

Me

(76) (77)

37.6.6 [NiXLn(?73-ALLYL)] COMPLEXES (n = 2, 3)*

The structure of the product of the reaction of the [NiX(L)(r73-allyl)] complexes with furtherligand molecules is dependent upon the nature of both X and the ligand and addition to give eithera five-coordinate species, e.g. (78) (equation 83), or an ionic species, e.g. (79) (equation 84), hasbeen observed.

+ p p h 3

Br

I-N i—PPh 3I

PPh3

(78)

(83)

[-4— NiBr) + 2S=C(NMe2)2 — • —{— Ni Br (84)

(79)

Other reactions leading to five-coordinate species include the insertion of CO2 into the Ni —Cbond of the nicklelacyclopentane derivative (80) (equation 85)139 and the reaction of butadienewith the nickel methyl complex (81) (equation 86),31 while the product of the reaction of 1,3-bis[o-(diphenylphosphino)phenyl]butene with nickel chloride is formulated as (82),69 and thatof the reaction of diphenylketene with [NiMe2(PMe2Ph)3] as the heteroallyl complex (83).56

Reaction of [(Ni(i73,T73-cot)}2] with triphenylphosphabenzene results in displacement of one ofthe cot rings to give a binuclear species formulated as (84).184 NMR investigations indicate thatin solution the allyl and alkene groups in this molecule exchange.

Cy2

Cy2

(80)

COi (85)

2[NiBr(Me)(PPri3)2] +

(81)

2 diphos (86)

/ N i \diphos Br


7]3-Allylnickel Complexes 173

(82)

PMe2Ph

—Ni—Me

PMe2Ph

(83) (84)

For completeness we should mention that one of the many products of the reaction of hexa-fluorobutyne with nickelocene has the composition [jNi(CF3C2CF3)(i7-C5H5)J4] and a structurein which one nickel atom interacts with an ?73-cyclopentenyl ring, a diene moiety and a secondnickel atom. The structure is shown on p. 90.4

Table 5 [NiXL2(7?3-Allyl)] and [NiL2(r73-Allyl)]+X- Complexes3

a Earlier work is tabulated and discussed in ref. 1, p. 360.

Cationic complexes are formed in the reaction of the [NiHL4]+ species with 1,3-dienes. Thekinetically formed product has an a/rtz-substituted 773-allyl group, suggesting that the diene adoptsa cis configuration on interaction with the nickel hydride. This then isomerizes to the thermo-dynamically more stable syn form (equation 87).177 A reaction probably related to this is thatof conjugated dienes with nickel chloride and zinc in the presence of triphenylphosphine.63 Otherroutes to cationic complexes include anion exchange, ligand exchange and the reaction of cationicallyl derivatives with nickel tetracarbonyl(equation 88).50'92-93

[NiHL4]+ -2L -NiHL2" (87)

[Ni(CO)4] + 2PPh3OP(NMe2)3ClO4

CIO4- + OP(NMe2)3 (88)

Complex Ref.

Neutral Complexes[NiBr(diphos)(773-2-MeC3H4)[ (86) 176[{NiBr(PPr'3)2}2(i?3,i73-C8HI2)] 31[{NiBr(diphos)}2(773,r;3-C8H12)] (87)a 31[NiCl(773-o-Ph2PC6H4CHCCMeC6H4PPh2-o)] (82) 69[Ni(PCy2C2H4PCy2)(7?3-2-O2CC3H4C3H4)] 139[NiMe(PMe2Ph)2(?73--Ph2CCMeO)] (83) 56[{Ni(PC5H2Ph3)2}2(7?

3,r73-cot)] (84) 184

Ionic Complexes[Ni(PPh3)2(773-C3H5)]ClO4 50,92Ni{P(OEt)3}2(773-l-MeC3H4)]PF6 36,46Ni(PPh3)2(7?

3-l-MeC3H4)]ZnCl3 50, 63, 92Ni(PPh3)2(r73-2-MeC3H4)]ClO4 50,92Ni(NCMe)2(r73-2-MeC3H4)]ClO4 92Ni(Me2NC=SNMe)2(r73-2-MeC3H4)] 93Ni(PPh3)2(7/3-2-PhC3H4)]ClO4 63,92Ni(NCMe)2(r;3-2-PhC3H4)]ClO4 50,92Ni(PPh3)2(?73-l,l-Me2C3H3)]ZnCl3 63Ni(PPh3)2(??3-l,2-Me2C3H3)]ZnCl3 63Ni(PPh3)2(r/3-l,l,2-Me3C3H2)]ZnCl3 (88) 47, 63{Ni(diphos)}2(773,r73-C8H, 2)] PF6 31Ni{P(OEt)3}2(cyc/o-C5H6D)]DSO4 190


The crystal structures of three [NiXL2(?73-allyl)] complexes (85)-(87) and of[Ni(PPh3)2(773-l,l,3-Me3C3H2)]+ZnCl3- (88) have been determined by X-ray methods.Comparison with the [NiX(L)(r?3-allyl)] complexes shows that the introduction of the secondligand molecule leads to an elongation of the Ni—X bond. This effect is so large in (85) that thiscomplex is best regarded as ionic.

Me

H2C2.06

2.04

(85)182

2.671

Br

(86)>87

pPh2

2.I8

H2C -CH "g"2.1^/

.42

H2.06

Ph2P

^CH2

Ni—Br

>Ph2

Me2.13^c

1.36,

Me i

Me

»

^PPh 3

2.235

2.220

PPh3

(88)47

(87)'75

37.6.7 [Ni(?y3-ALLYLXr7-CYCLOPENTADIENYL)] COMPLEXES*

This class of complex can be conveniently prepared by reacting nickelocene with an alk-2-enylGrignard reagent(equation 89).71'91 Alternatively, nickelocene can be reacted with isopropyl-or isobutyl-magnesium halide in the presence of a diene (equation 90): elimination of propeneor butene leads to generation of a nickel hydride species which adds to the complexed alkene.91

Related to this is the reaction of nickelocene with alk-3-enyl Grignard reagents (equation 91):diene elimination results in the formation of the intermediate nickel hydride.147 A combinationof the reaction sequences shown in equations (90) and (91) accounts for the formation of 7j3-al-lylnickel complexes in the reaction involving nickelocene, isopropylmagnesium bromide and anon-conjugated diene:158 the primary product is a nickel alkenyl species which, in the case of thealk-3-enyl homologue, reacts further in a manner analogous to that shown in equation (91). (Thenickel alk-4-enyl complexes are stable and are discussed in Chapter 37.4).


[Ni(77-C5H5)2] + ^ k / M g B r —• -^—Nifa-CsHs)- + C5H5MgBr (89)

rj3 -A I ly I nickel Complexes 17 5

[Ni(r/-C5H5)2] + Me2CHMgBr +

(77-C5H5)Ni-V- (90)CHMe2 C H .H

[Ni(,-C5H5)2] + ^ ^ ^ M g B r ^ ^ ^

(7;-C5H5)Ni

d7-C5H5)Ni-J + U-C 5 H 5 )Ni^ (91)

Related to these reactions is the thermal or photochemical conversion of the ligand-stabilizednickel but-3-enyl complexes [NiCH2CH2CH=CH2(L)(77-C5H5)] (L = CO, PPh3) to [Ni(r;3-l-MeC3H4)(r;-C5H5)].24'25 What can be regarded as the reversal of this reaction (the ligand-induced conversion of an r;3-allyl group into the V -allyl form) has been suggested to occur upontreatment of [Ni^-CaHsXty-CsHs)] with excess trialkyl phosphite. The formation of[Ni{P(OR)3J4] in this reaction follows a third-order rate law.6

The product of the reactions discussed above is normally a mixture of isomers (equation 92)differing in the arrangement of the substituents (syn or anti), e.g. (89) and (90), or in their positions(91). Prolonged heating causes isomerization. In our example, the original 42:58 ratio of (89): (90)changes to 87:13 after maintaining the mixture in THF at 90 °C for three weeks. At highertemperatures isomerization of the allyl skeleton occurs to give the thermodynamically more stablesystem: after 10 days at 120 °C in THF, 79% of (91) isomerizes to a mixture of (89) and (90).These reactions probably proceed through the intermediacy of a hydridonickel diene species similarto those shown in equations (90) and (91).

Me2CHMgBr

(7?-C5H5)Ni-V- + (*7-C5H5)Ni^- + (*-C5H5)Ni^ (92)

(89) (90) (91)

T]3~Allylnickel ?7-cyclopentadienyl complexes may also be prepared by reacting sodium cyclo-pentadienide with an r/3-allylnickel halide (equation 93).l More exotic examples prepared by this

[{NiBr(773-C3H5)!2] + 2C5H5Na —* 2[Ni(773-C3H5M>7-C5H5)] + 2 NaBr (93)

method include the dihydropentalenylene complex (92) (equation 94)7 and (93), which is theproduct of a disproportionation reaction (equation 95).160 Crystal structure determination showsthat in both (92) and (93) the dihedral angle between the allyl and cyclopentadienyl planes is ca.18°. This angle of tilt is reproduced in a CNDO description of the bonding in [Ni^-CsHsXr;-C5H5)], which also confirms that interaction between the nickel and allyl group involves mainlythe terminal C atoms of the organic group.24'28

[Ni(77-C5H5)2]


Table 6 [Ni(?73-Allyl)(T7-Cyclopentadienyl)] Complexes3

Li2C8H6

Ni-V—/-PdCl + 4 NaC5H5

( 9 4 )

2.079

2.087

[{Pd(J7-C5H5))2(C6H8)]

Ni\ (

\

1.965

1.978

r o 2'A 1.41

H2<

CH2

1.401L

1.398m -I

^O/l.394

^1.423

(95)

(93)

?73-Cyclobutenylnickel complexes can be prepared by nucleophilic attack at a metal-bonded

cyclobutadiene group (equations 96, 97)x whereby the substituents adopt an exo position.

Ph

NaOMe

HBr MeO- : - N i d ? - C 5 H 5 ) (96)

TJ3-AllyI group Ref.

C 3 H 5a b 6 ,10 ,91,114,159, 164

l-MeC3H4a 31 ,24 ,25 ,71 ,91 ,147 ,158 ,159

l-EtC3H4 91l-Pr iC3H4 912-MeC3H4 91, 159l, l-Me2C3H3 91, 158, 159l,2-Me2C3H3 91,158l,3-Me2C3H3 91,158,159l,2-Me,EtC3H3 91, 158l,2-Me,Pr iC3H3 91l,l ,3-Me3C3H2 91l,2,3-Me3C3H2 91,158l,l,3-Me2,Pr iC3H2 158l,3,3-Me2Pr iC3H2 158l,l,3,3-Me4C3H 91l,l,2,3-Me3EtC3H 158cyclopentenyl3 38,134,158cyclooctadienyl (95) 39[{Ni(n3-C3H5)}2(77-C8H6)] (92)* 7[{Ni(r7-C5H5)}2(r/3-C6H8)] (93) 91

a Earlier work is discussed and tabulated in ref. 1, pp. 367-372. b [Ni(r;3-C3H5)(77-PriC5H4)].114

rji-AIIylnickel Complexes 177

Me

G- —NiCl2 +• 2NaC5H5-2NaCl (97)

2.10 2.11

773-Cyclopentenylnickel complexes have been prepared by the 1,2-addition of hydrogen, afluoroalkene or alkynes to one of the rings of nickelocene (equations 98, 99).1'38 [Ni(r73-C5H7)-(77-C5H5)] is also formed in a variety of related reactions (see ref. 1, p. 371) which include thatof cyclopentadiene with nickel vapour, of nickel bromide with cyclopentenylmagnesium bromideand of nickelocene with isopropylmagnesium bromide in the presence of cyclopentadiene;158 itis also a side product of the electrochemical reduction of nickelocene.134

[Ni(i7-C5H5)2] + H2

[Ni(7,-C5H5)2] + CF 2 =CF 2

(98)

(99)

An r73-cyclooctadienyl complex has been prepared by reacting the cationic 1,5-cycloocta-dienenickel species (94) with methoxide (equation 100): the alkenyl complex (95) is first formedand reacts further with elimination of methanoL39

OMe"

(94)

\NK17-C5H5)

oMe

(95)

-MeOH(100)

37.6.8 ?;3-CYCLOPROPENYLNICKEL COMPLEXES

The cyclopropenyl cation is the simplest aromatic system and differs from the r/3-allyl groupin the antibonding character of the non-bonding orbital. A series of complexes analogous to thoseformed by the r/3-allyl system have been isolated, e.g. [(NiBr(r/3-Ph3C3)i2], [NiCl(py)2(r7

3-Ph3C3)]and [Ni(773-Ph3C3)(?7-C5H5)]. Complexes of the type [Ni(7?3-R3C3)2] are, however, still unknown(see ref. 1, p. 373). These complexes have been prepared by orthodox organometallic procedures(equations 101, 102, Scheme 2). A series of [NiClL2(r;3-Ph3C3)] complexes have also been pre-pared by addition of a variety of ligands, e.g. CO, THF, PPh^Me, to the monocarbonyl complex(96; X = Cl).75

[Ni(cod)(77-C5H5)]+

178 T]3-Allylnickel Complexes

2[Ni(cod)2] + 2Ph3C3Br —- [jNiBiV-Ph3C3)}2] + 4 cod (101)

[Ni(CO)4] + Ph3C3Cl ^ ^ [NiCl(CO)(^3-Ph3C3)]

(96)

Ph i.4i^K^ — \ i 43J ^ K r T,cH

? ^^\ -ph

' N i \ 2 0 4 N i

Cl2.14

(97) (98)

Scheme 2

Ph3P io7.4°vPPh32.234\ ^2.242

Ni[Ni(PPh3)2(CH2=CH2)] + Ph3C3+ClO4- _CH'!!CH2> 2 . 0 7 ^ 7 V 9 1 PF6" (102)

(99)

The crystal structures of (97) and (98) have been determined by X-ray methods.161'162 In bothcomplexes the C—C bond in the three-membered ring is ca. 0.05 A longer than that found in thefree ligand. The three phenyl groups are tilted away from the nickel by ca. 20°, those in (98) beingarranged in a propeller-like manner. The cyclopropyl ring in (99) is not symmetrical, one bondhaving considerable double bond character.192

An INDO SCF MO calculation for [NK^-C^Xrj-CsHs)] 7 6 ' 1 0 0 ' 1 0 1 indicates that there isa substantial transfer of charge from the metal to the r;3-cyclopropenyl group while that fromthe ligand to the metal is of only minor importance. The greater involvement of the orbitals ofthe C3H3 ring than those of the C5H5 ring in the bonding is consistent with the shorter (0.14 A)Ni—C bond formed to the three-membered ring.

It is appropriate to mention here the complexes formed by cyclotriphosphorus or cyclotriar-senic.77"79'185 Reaction of hydrated nickel salts with the tridentate ligand MeC(CH2Ph2P)3 andwhite phosphorus or yellow arsenic leads to the formation of complexes having the composition[Ni((PPh2CH2)3CMe}]2M32+ (M = P, As) and a structure, e.g. (100) (equation 103), in whicha cyclo-triphosphorus or -triarsenic fragment is bonded as a 773-ligand to both metal atoms. Mixedmetal complexes of nickel and cobalt or rhodium have also been isolated (equation 104, M = Co,Rh).

C\^^Z\ /)2(PPh2C2H4)3CMe + P3 — (103)

(100)

2Ni2+

7]3 -A IlyInickel Complexes 179

[Mj(PPh2CH2)3CMe|(7?3-P3)] + Ni2 + + (PPh2CH2)3CMe — •

[MeC(CH2Ph2P)3M(i;3-P3)Ni(PPh2CH2)3CMe]2+ (104)

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