[Advances in Organometallic Chemistry] Advances in Organometallic Chemistry Volume 60 Volume 60 ||...

CHAPTER TWO

Supramolecular Self-assemblyof Transition Metal CarbonylMolecules Through M–CO(LonePair). . .p(Arene) InteractionsJulio Zukerman-Schpectora,�, Ionel Haiducb,�, Edward R.T. Tiekinkc,�aLaboratorio de Cristalografia, Estereodinamica e Modelagem Molecular, Departamento de Quımica,Universidade Federal de Sao Carlos, Sao Carlos, SP, BrazilbFacultatea de Chimie, Universitatea Babes-Bolyai, Cluj-Napoca, RomaniacDepartment of Chemistry, University of Malaya, Kuala Lumpur, Malaysia�Corresponding authors: e-mail address: [email protected]; [email protected];[email protected]

Contents

1.

AdvISShttp

Introduction

ances in Organometallic Chemistry, Volume 60 # 2012 Elsevier Inc.N 0065-3055 All rights reserved.://dx.doi.org/10.1016/B978-0-12-396970-5.00002-5

50
2. Data Mining 53 3. Supramolecular Aggregation Based on M–CO(Lone Pair). . .p(Arene) Interactions 54
3.1
Motif A 54 3.2 Motif B 56 3.3 Motif C 61 3.4 Motif D 65 3.5 Motifs E, F, and G 67 3.6 Motifs H and I 76 3.7 Motif J 79 3.8 Motif K 80
4.
Thio- and Selenocarbonyl Analogues 81 5. Strength and Correlations 82 6. Conclusions and Outlook 83 Acknowledgments 83 References 84
49

http://dx.doi.org/10.1016/B978-0-12-396970-5.00002-5

50 Julio Zukerman-Schpector et al.

1. INTRODUCTION

Classical organometallic chemistry concentrates largely on molecular

structure. Until recently, the chemists working in the field were satisfied

with establishing the structure of their molecules, particularly when this

was possible with the aid of single crystal X-ray diffraction, which was often

considered the ultimate proof. The phenomenal progress of chemical crys-

tallography made possible rather precise determination of the arrangements

of molecules in the crystal (crystal packing) and frequently revealed architec-

tures determined by intermolecular forces, weaker than covalent bonds, but

strong enough to maintain the molecules associated into organized struc-

tures. This has been known for quite some time in organic chemistry, where

intermolecular association through hydrogen bonds has traditionally been

well documented. The extended study of intermolecular association gave

birth to supramolecular chemistry, which has become a field of intense de-

velopment in the last few decades.

Supramolecular chemistry is the discipline covering “the chemistry of

molecular assemblies and of the intermolecular bond” and deals with

“organized entities that result from the association of two or more chemical

species held together by intermolecular forces.” It operates with two types of

“objects”: supermolecules, that is, “well-defined oligomolecular species that

result from the intermolecular association of a few components,” and mo-

lecular assemblies or supramolecular arrays, which are “polymolecular systems

that result from the spontaneous association of a non-defined number of

components.”1

There is a broad variety of noncovalent intermolecular forces2 able to

hold together the molecular building units (also called “tectons”) in a crystal

and even in solution, leading to supramolecular association.3 Examples of

such noncovalent interactions include hydrogen bonds,4 dative coordinate

bonds,5 p–p stacking,6 secondary bonds (“soft–soft” interactions)7 or

cation–p interactions,8 and other types of less well-defined interactions

(electrostatic forces, etc.). The supramolecular structures are formed spon-

taneously, and the process is known as self-assembly.

In recent years, some new synthons which can act as intermolecular

bonding motifs for the formation of supramolecular structures have

emerged. These include anion. . .p(arene) interactions,9 cation. . .p(arene)interactions (alkali metals),10 nonmetal lone pair. . .p(arene) interactions,11

C–H. . .p(arene) interactions,12 and C–H. . .p(chelate ring) interactions in

51M–CO(Lone-Pair). . .p(Arene) Interactions Assembling Transition Metal Compounds

metal complexes.13 It has been shown that metal and semi-metal lone pair. . .p(arene) interactions occur in arenederivativesofmain groupelements in low

oxidation states, and that these lead to well-defined supramolecular

architectures. Thus, bibliographic surveys have appeared, describing supra-

molecular structures based on lone pair. . .p(arene) interactions for, in chro-nological order, tellurium(II) and tellurium(IV),14 tin(II),15 lead(II),16 arsenic

(III)17, and selenium(II) and selenium(IV).18 Metal. . .p(arene) interactionswere also reported in gold(I) and gold(III) compounds,19 and anion andmet-

al. . .p(heteroaromatic ring) interactions in both light-20 and heavy-21 atom

crystal structures. As described in the original surveys,many of these synthons

stabilize a range of supramolecular architectures of varying dimensionalities.

The general concepts of supramolecular chemistry obviously apply to

organometallic chemistry as well, generating the discipline of supramolecu-

lar organometallic chemistry.22 Naturally, all of the aforementioned inter-

molecular noncovalent forces can be encountered in organometallic

compounds. Over and above these, organometallic compounds afford some

specific interactions.

A bonding motif specific to “organometallic chemistry” includes bonds

between metals and unsaturated organic molecules, that is, metal–p interac-

tions. Cyclopentadienyl–metal p complexes (e.g., metallocenes and related

compounds) are typical for transition metals but some main group deriva-

tives are also known.23 When acting intermolecularly, as a bonding motif

for supramolecular self-assembly, the metal. . .p-cyclopentadienyl bonds

can be observed in the structures of bis(cyclopentadienyl)lead(II) or

“plumbocene,” [Pb(Z5-C5H5)2]n (n¼6 or 1), which forms both cyclic

hexameric supermolecules and helical supramolecular chains,24 or with

the supramolecular structures of [(Z5-C5Me5)SbCl2]n.25 In both types of

compound, the metal atoms alternate with five-membered cyclopentadienyl

rings, that is, . . .M. . .(p-Cp). . .M. . .(p-Cp). . .. These metal–p bonds are

weaker than comparable bonds in transition metal cyclopentadienyls, as

illustrated by longer interatomic distances from the metal to the C5 ring

centroid: Pb. . .centroid(Cp) (2.59–3.54 A) and Sb. . .centroid(Cp)(3.41–3.58 A),26 compared to 1.90–2.70 A, which is the normal range of

metal–centroid distances in metallocenes.

Benzene rings form numerous Z6-aryl metal complexes with transition

metals, for example, dibenzene-chromium Cr(C6H6)2 and benzene-

chromium tricarbonyl C6H5Cr(CO)3, and are formed by contribution of

the p-electrons from the organic molecule into the empty d-orbitals of

the metal, with the aim of achieving a noble gas configuration.


We are interested in exploring the presence and implications of metal

(lone pair). . .p(arene) interactions as bonding motifs for supramolecular

self-assembly.14–19,21 Such structures can be identified by data mining of

the Cambridge Crystallographic Database27 by checking for short contacts

between the metal atoms and the aromatic rings. It should be underscored

that in the published works analyzed here, the authors (with very few

exceptions) have established only the molecular structure and did not

examine the packing of the molecules in the crystal. Thus, the

supramolecular self-assembly was often overlooked.

As a continuation of this interest, an examination of structures containing

metal carbonyl moieties and arene groups, as recorded in the Cambridge

Crystallographic Database,27 has been undertaken to evaluate the propensity

of M–CO(lone pair)....p(arene) interactions and, when formed, the nature

of the resulting supramolecular architecture based on these. Only M–CO

(lone pair). . .p(arene) interactions operating in isolation from other supra-

molecular synthons are discussed in the following, with no attempt to give a

full discussion of the complete crystal packing in three dimensions.

This workwas prompted by the knowledge that a lone pair of the oxygen-

containing sites of various (macro)molecules is able to interact with the arenes

(or aryl groups). Thus, very precise X-ray structure analyses showed that the

oxygen lone pair of a water molecule interacts with the cytosine base site in

DNA.28 Further, in 286 protein structures out of the 500 investigated,

carbonyl oxygen atoms were close, within a distance of 3.5 A, to aromatic

centers, suggesting a stronger interaction than a van der Waals contact.29

The oxygen(lone pair). . .p(arene) interaction has been discussed in some

detail30 and examples cited, indicating that the oxygen atoms providing the

lone pair in such interactions can be present in water,28,31 ether,32 or carbonyl

moieties.33 In a quantitative theoretical study of interactions between oxygen

(lone pair) and aromatic rings, it was demonstrated that even electron-rich

aromatic rings and oxygen lone pairs exhibit attractive interactions.34

This information suggested that transition metal carbonyl compounds,

containing arene groups in their structures, could be interesting candidates

for oxygen(lone pair). . .p(arene) interactions. The M–CO moiety is linear

and the lone pair at the oxygen is favorably oriented to point perpendicularly

to the centroid of an aromatic ring. The bonding between transition metal

centers and carbon monoxide is well understood,35 but the potential supra-

molecular interactions involving metal-bound carbonyl ligands have not

been explored in detail so far. Here, we discuss supramolecular aggregation

patterns based on M–CO(lone pair). . .p(arene) interactions. A preliminary

report of this work was published recently.36


2. DATA MINING

A search of the Cambridge Crystallographic Database (CSD version

5.32 and three updates)27a using the data interrogation program CON-

QUEST was undertaken.27b The details of the search conducted are shown

in Fig. 2.1. Three geometric parameters were employed, that is, a distance d

(the distance between the centroid of the arene ring (Cg) and the O center),

an angle a (defined by the vector perpendicular to the arene ring (V1) and the

vector passing from the O atom to the centroid of the arene ring), and a sec-

ond angle b (the C–O. . .Cg angle). The distance restriction was d�3.8 A, a

distance based on the sum of the half-thickness of an arene ring (half the

centroid. . .centroid distance in parallel phenyl rings¼1.7–1.9 A)37 and

the van der Waals radius of O, taken as 1.52 A,38 plus 10% to ensure that

all potential “hits” were investigated. To ensure the O(lone pair) was di-

rected toward the center of the ring, rather than to the periphery, a was

�20�. Finally, bwas restricted to lie in the range 160–180� in order to focusupon terminally bound carbonyls rather than (semi)bridging carbonyls.

A total of 17,540 metal carbonyl structures have been deposited in the

CSD.27 After excluding duplicates, structures flagged with errors, and those

with disorder, approximately 100 structures satisfied the search criteria and

were manually evaluated (using crystallographic software ORTEP,39a

DIAMOND39b, and PLATON39c) for the presence of M–CO(lone

pair). . .p(arene) interactions in isolation of other supramolecular synthons

operating in the same dimension(s). A total of 85 structures satisfied the

Cg

O

d

b

a

C

[M]

V1

V2

Figure 2.1 Diagram illustrating the search protocol to determine the presence of pu-tative M–CO(lone pair). . .p(arene) interactions. The parameter d is the distance betweenthe ring centroid of the arene ring (Cg) and the O atom (corresponding to vector, V2).V1 is the vector normal to the plane through the arene ring. a is the angle between theV1 and V2 vectors. b is the C–O. . .Cg angle.


above search criteria and so feature supramolecular synthons based on

M–CO(lone pair). . .p(arene) interactions. Details of the supramolecular ar-

chitectures sustained by these are given below.

3. SUPRAMOLECULAR AGGREGATION BASED ON M–CO(LONE PAIR). . .p(ARENE) INTERACTIONS

The 85 structures deemed to feature M–CO(lone pair). . .p(arene)interactions lead to 11 supramolecular motifs (A–K), as detailed below.

Four of the motifs (A–D) are zero-dimensional, the majority (E–L) are

one-dimensional, and there is a sole example of a three-dimensional archi-

tecture (motif K) sustained by M–CO(lone pair). . .p(arene) interactions.Geometric data characterizing these interactions are given in the tables.

For each motif, entries are arranged in increasing order of d. Chemical

diagrams are given for each structure, conforming to a specific supramo-

lecular motif; only interacting species are included so that additional

species, typically solvent, are omitted. Normally, only one example of each

motif is illustrated. Diagrams are original and were generated using DIA-

MOND39b with arbitrary spheres; hydrogen atoms, except for hydrides

and acidic hydrogens, have been omitted.

3.1. Motif AMotif A is a zero-dimensional, two-molecule aggregate whereby two like

molecules are connected via a single M–CO(lone pair). . .p(arene) interac-tion. A total of four structures, 1–4,40–43 adopt this motif. Geometric data

are collected in Table 2.1. The common feature of these crystal structures is

that there are multiple molecules in the crystallographic asymmetric unit

and that these are connected by a single M–CO(lone pair). . .p(arene)interaction. A representative aggregate is shown for 443 in Fig. 2.2.

Even from this small sub set, an enormous structural diversity in the

structures featuring a M–CO(lone pair). . .p(arene) interaction is apparent,

Table 2.1 Geometric data characterizing M–CO(lone pair). . .p(arene) interactions inzero-dimensional motif A: two-molecule aggregate sustained by a single interactionCompound/Reference d (Å) a (�) b (�) Metal

1 (40) 3.26 9.9 173.5 Co

2 (41) 3.35 7.1 163.2 Fe

3 (42) 3.45 0.6 162.5 Os

4 (43) 3.52 7.6 161.2 Mo

O

OO

O O

O

OO

P

P

Mo

Figure 2.2 An exemplar of zero-dimensional motif A: a two-molecule aggregate in 443

sustained by a single M–CO(lone pair). . .p(arene) interaction.


that is, fourdifferentmetals,mono-, tri-, andtetra-nuclear species, andnumbers

of carbonyls ranging from 4 to 12. Similar comments pertain to an even greater

extent in motifs with more numerous representatives.


3.2. Motif BMotif B describes zero-dimensional two-molecule aggregates connected

by a pair of M–CO(lone pair). . .p(arene) interactions. A total of 22 struc-

tures, 5–26,44–65 feature this motif and geometric parameters

characterizing these interactions are collated in Table 2.2. A common

Table 2.2 Geometric data characterizing M–CO(lone pair). . .p(arene) interactions inzero-dimensional motif B: two-molecule aggregate sustained by two interactionsCompound/Reference d (Å) a (�) b (�) Metal

5 (44) 2.94 4.3 165.1 Ru

6 (45) 3.12 6.9 160.3 Mo

7 (46) 3.25 6.1 161.2 Ir

8 (47) 3.26 5.4 160.0 Rh

9 (48) 3.27 3.3 169.3 Ru

10 (49) 3.28 6.9 176.0 Fe

11 (50) 3.30 6.5 161.8 Re

12 (51) 3.32 2.9 161.9 Fe

13 (52) 3.35 5.0 166.7 W

14 (53) 3.37 8.3 174.5 Ru

15 (54) 3.40 8.5 168.2 Ru

16 (55) 3.42 0.3 172.8 Cr

17 (56) 3.50 7.4 167.7 Fe

18 (57) 3.51 9.5 164.9 Ir

19 (58) 3.52 1.6 174.1 Os

20 (59) 3.55 5.9 168.1 Ru

21 (60) 3.57 3.9 162.1 Fe

22 (61) 3.60 8.5 174.5 Fe

23 (62) 3.65 9.5 162.7 Re

24 (63) 3.70 8.2 168.3 Fe

25 (64) 3.75 6.2 161.2 Fe

26 (65) 3.36 5.5 179.3 Fe


feature of the structures adopting motif B is the presence of symmetry

within the two-molecule aggregates. In all but one example, the

molecules are connected over a center of inversion. A representative

structure, that is, 1958, is shown in Fig. 2.3A. The odd structure is that

of 2665 where the molecules are related by a twofold rotation axis; this

is illustrated in Fig. 2.3B.

O

OO

O

O

O

O

O

O

O

Fe

Fe

O

O

O O

P

A

B

P

P

Os

Os OsSi

Figure 2.3 Exemplars of zero-dimensional motif B: a two-molecule aggregate issustained by two M–CO(lone pair). . .p(arene) interactions: (A) centrosymmetric 1958

and (B) 26,65 where the dimeric aggregate has twofold symmetry.


3.3. Motif CMotif C is closely related to motif A in that two species are connected by a

single M–CO(lone pair). . .p(arene) interaction. The difference occurs in

that for motif A, the molecules are the same whereas for motif C, the inter-

acting molecules are distinct. In fact, only ionic species adopt motif C


comprising [Ph4P]þ (2 examples) or [Ph3P¼¼N¼¼PPh3]

þ (10 examples)

cations with carbonyl-containing anions, 27–3866–77; geometric data are

listed in Table 2.3. Therefore, each M–CO(lone pair). . .p(arene)interaction involves an anion-bound carbonyl connected to a cation-

bound phenyl group as exemplified in Fig. 2.4 for 38.77

Ir Ru

RuRu

N PPh3PPh3 Ph3PPh3P

PPh3Ph3P

PPh3Ph3PPPh3Ph3P

PPh3Ph3P

+

CO

(27)

(32)(31)

(30)(29)

(28)

CO

COCOOC

Ph

OC

OC

OC

OC CO

CO_

Co Fe

OC

CO

COCO

OC

OC CO

CO_

N+

Fe Fe

OC

COOC

OC CO

CO_

N+

OC

CO

HCr Cr

HS

COOC

OC CO

CO_

N+

OC

CO OC

Fe

Fe

Fe

CO

CO

OC

OC COO

CO

COMe

COOC

OC

N+

_W Re

CO

COCO

OC

OC CO

CO_

N+

CO

CO

CO CO


Fe Fe

Fe

Fe

Hg

COOC

CO

COCOOC

OC

OC

OC

CO

CO

COOC

_

Fe Fe

Fe

Te Te

OC CO

IOC

CO

CO

CO

OC

OC

OC

_

+

Ru Ru

RuRu

Ru

Ru

Br

C C

COOC

COCO

OC

OC

OC CO

COOC

COOC CO

CO_

N P(p-tol)3P(lot-p)3

+

Ni Ru

Ru

H

OC CO

COOC

CO

CO

_

RuCC

C

C

COOC

Fe

Fe

Bi Bi

Fe

Fe

CO

CO

CO

COFe

CO

CO

OC

OC

COCOOC

OCOC CO

COOC CO

N+

Mo

N

N

OC

OC

S

SN

Et

Et

O

N

N

N+

N+

+

_

OO

OO

O

O

Ph3P PPh3

2 [PPh3 PPh3]Ph3P PPh3

PPh4

PPh4

(38)

(37)

(36)

(35)

(34)

(33)

S

S

O

O

P

P

N

O

N

N

NNN

Mo

Figure 2.4 Exemplar of zero-dimensional motif C: a two-molecule aggregate in 3877

sustained by a M–CO(lone pair). . .p(arene) interaction occurring between dissimilarspecies.

Table 2.3 Geometric data characterizing M–CO(lone pair). . .p(arene) interactions inzero-dimensional motif C: two-molecule aggregate sustained by a single interactionbetween dissimilar speciesCompound/Reference d (Å) a (�) b (�) Metal

27 (66) 3.13 9.8 171.4 Ru

28 (67) 3.21 2.4 165.8 Fe

29 (68) 3.42 2.4 161.9 Fe

30 (69) 3.47 8.2 169.4 Cr

31 (70) 3.50 5.0 168.3 Fe

32 (71) 3.55 7.0 168.3 W

33 (72) 3.66 7.2 163.1 Fe

34 (73) 3.58 2.6 167.9 Fe

35 (74) 3.66 8.8 164.5 Ru

36 (75) 3.73 7.6 167.3 Ru

37 (76) 3.77 6.6 161.6 Fe

38 (77) 3.80 5.6 173.6 Mo



3.4. Motif DMotifD represents the final variation on zero-dimensional aggregates based

on M–CO(lone pair). . .p(arene) interactions and features a three-molecule

aggregate sustained by two such interactions. Eight examples, 39–46,78–84

adopt this motif and geometric parameters describing these are collected

in Table 2.4. While the common feature of all structures is that they are

ionic, seven resemble motif C in that a carbonyl-bearing cation interacts

with two phenyl groups derived from two [Ph4P]þ cations; each three-

molecule aggregate is centrosymmetric; 4078 is illustrated in Fig. 2.5(A).

The odd structure adopting this motif is that of 46,84 as illustrated in

Fig. 2.5(B); the species has twofold symmetry. Here, two phenyl groups

of a complex dication function as acceptors for two M–CO(lone

pair). . .p(arene) interactions where each carbonyl is part of a rhodium-

containing anion.


Table 2.4 Geometric data characterizing M–CO(lone pair). . .p(arene) interactions inzero-dimensional motif D: three-molecule aggregate sustained by two interactionsbetween dissimilar speciesCompound/Reference d (Å) a (�) b (�) Metal

39 (78) 2.97 2.0 166.1 W

40 (78) 3.05 3.4 163.9 Cr

41 (79) 3.20 8.8 164.9 Re

42 (80) 3.35 4.7 165.2 Fe

43 (81) 3.36 9.9 163.0 Fe

44 (82) 3.46 1.8 162.4 Fe

45 (83) 3.49 9.6 163.5 Mo

46 (84) 3.22 5.8 172.5 Rh

O

O

O

OO

O O

O

O

O

P

A

B

Rh

S

N

O

ORh Cl

ClN

OO

Cr

Cr

Sn

Figure 2.5 Exemplars of zero-dimensional motif D: a three molecule aggregatesustained by two M-CO(lone pair). . .p(arene) interactions occurring between dissimilarspecies in (A) 4078 having a center of symmetry, and (B) 4684 having twofold symmetry.


3.5. Motifs E, F, and GMotif E is the most numerous and first of five motifs that adopt one-

dimensional aggregation patterns. A total of 20 structures, 47–66,85–103

form linear supramolecular chains sustained by an average of one M–CO

(lone pair). . .p(arene) interaction per molecule, that is, forming one

acceptor and donor contact; see Table 2.5 for geometric parameters.

Motif E is exemplified by 5795 in Fig. 2.6. The structure of 4785 is

notable in that the Os–CO(lone pair). . .p(arene) interaction distance of

2.89 A is the shortest of the structures surveyed herein.


Table 2.5 Geometric data characterizing M–CO(lone pair). . .p(arene) interactions inone-dimensional motif E: linear chain sustained by a single interactionCompound/Reference d (Å) a (�) b (�) Metal

47 (85) 2.89 7.7 173.9 Os

48 (86) 3.09 1.5 171.7 Fe

49 (87) 3.15 7.6 166.6 Os

O O

OO

OO

O

O P

P MnMn

Au

Figure 2.6 Exemplar of one-dimensional motif E: linear supramolecular chain in 5795

sustained by one M–CO(lone pair). . .p(arene) interaction per molecule.

Table 2.5 Geometric data characterizing M–CO(lone pair). . .p(arene) interactions inone-dimensional motif E: linear chain sustained by a single interaction—cont'dCompound/Reference d (Å) a (�) b (�) Metal

50 (88) 3.16 7.8 167.1 Mo

51 (89) 3.17 7.8 173.3 Co

52 (90) 3.18 3.9 162.0 Ir

53 (91) 3.24 8.8 170.3 Os

54 (92) 3.26 5.9 164.5 Co

55 (93) 3.30 6.1 163.6 Os

56 (94) 3.33 7.8 163.5 Re

57 (95) 3.35 5.8 164.3 Mn

58 (96) 3.36 8.4 163.8 Re

59 (97) 3.43 3.6 179.2 Os

60 (98) 3.45 3.2 163.2 Re

61 (97) 3.46 3.5 179.5 Ru

62 (99) 3.47 6.4 169.7 Re

63 (100) 3.52 9.9 163.3 Ru

64 (101) 3.67 3.6 161.7 Ru

65 (102) 3.67 9.5 165.2 Ru

66 (103) 3.70 8.6 177.1 Cr



Motif F is found in eight crystal structures, 67–74,104–111 and is again a

supramolecular chain like motif E but with a helical topology in which a

molecule participates in a single acceptor and single donor interaction.

Geometric data are summarized in Table 2.6, and a representative

example is shown in Fig. 2.7 for 71.108


Table 2.6 Geometric data characterizing M–CO(lone pair). . .p(arene) interactions inone-dimensional motif F: helical chain sustained by a single interactionCompound/Reference d (Å) a (�) b (�) Metal

67 (104) 3.10 7.1 174.8 Re

68 (105) 3.19 4.5 177.1 W

69 (106) 3.20 6.9 171.4 Ru

70 (107) 3.25 7.6 169.8 Fe

71 (108) 3.52 7.0 166.5 W

72 (109) 3.52 8.0 178.9 Ru

73 (110) 3.56 2.5 175.9 Ru

74 (111) 3.73 9.2 162.9 Os

O

O

O

O

O

W PP

O

Figure 2.7 Exemplar of one-dimensional motif F: helical supramolecular chain in 71108



MotifG, found in five crystal structures is, as for each of motifs E and F,

sustained by one acceptor and one donor M–CO(lone pair). . .p(arene) in-teraction per molecule leading to a supramolecular chain with a zigzag to-

pology. Structures 75–79112–116 adopt this motif. The geometric parameters

characterizing these are given in Table 2.7 and an example is illustrated in

Fig. 2.8 for 78.115

Ru Ru

PhPh

H

Ru

CO

CO

CO

OC

OC

OC

Pt Pt

Pt

Ru Ru

Ru

H

CO

COOC

COOC

OC

OC CO

CO

CO

COOC

OC CO

(75)

Ru

Ru

Ru

Ru

Ru

Ru

O OC

OC

O

COCO

O

CO

CO

CO

CO

OC

OC

OC

Pt

Pt

PtO

P

P

Ph2

Ph2

Ph2P PPh2

O

(77)


Ph2P

WH

W

PPh2

COOC

COOC

CO

CON

P(H)Ph2

O

(79)

FeFe

Ph2P

OC

OC

CO

CO

PPh2

(76)

S

Ph

Mn

Mn

SeSe

COCOOC

COOC CO

MnMn PP

OC CO

OC COOC CO

COOC

Ph

Ph

Ph

Ph

(78)

O

Table 2.7 Geometric data characterizing M–CO(lone pair). . .p(arene) interactions inone-dimensional motif G: zigzag chain sustained by a single interactionCompound/Reference d (Å) a (�) b (�) Metal

75 (112) 3.06 8.8 162.0 Ru

76 (113) 3.20 9.4 169.1 Fe

77 (114) 3.23 6.7 174.9 Ru

78 (115) 3.27 7.5 169.4 Mn

79 (116) 3.50 7.9 173.3 W

O

OO

O

OO

O OO

OO O

OO

O

P

P

Se

Se

MnMn

Mn

Mn

Figure 2.8 Exemplar of one-dimensional motif G: zigzag supramolecular chain in 78115



3.6. Motifs H and IMotif H is a linear supramolecular chain sustained by an average of two

M–CO(lone pair). . .p(arene) interactions per molecule, that is, each mole-

cule participates in two acceptor and two donor contacts. Three structures

adopt this motif, 80–82,117–119 and that of 80117 illustrated in Fig. 2.9.

Geometric data are listed in Table 2.8. Table 2.8 also contains geometric

data for 83,120 the sole example of a structure adopting motif I, a

supramolecular chain with a zigzag topology sustained by two M–CO

(lone pair). . .p(arene) interactions per molecule (Fig. 2.10).


Table 2.8 Geometric data characterizing M–CO(lone pair). . .p(arene) interactions inone-dimensional motif H: linear chain sustained by two interactions, and motif I: zigzagchain sustained by two interactionsCompound/Reference d (Å) a (�) b (�) Metal

Motif H

80 (117) 3.03 1.0 177.2 W

81 (118) 3.25 3.9 162.2 Cr

3.33 7.4 164.5 Cr

82 (119) 3.49 6.1 173.5 Re

Motif I

83 (120) 3.20 9.1 167.2 Os

O

O

O

FF

FF

F

F

N

N

N

W

F

F

F

F

FF

F

F

F

Figure 2.9 Exemplar of one-dimensional motif H: linear supramolecular chain in 80117

sustained by two M–CO(lone pair). . .p(arene) interactions per molecule.


OO

OO

O

O

O

O

O

O

O

O

O O

O

Os

Os

Os Os

Os

Figure 2.10 One-dimensional motif I: zigzag supramolecular chain in 83120 sustainedby two M–CO(lone pair). . .p(arene) interactions per molecule.


3.7. Motif JMotif J is adopted by a sole example, 84.121 The ionic structure comprises

carbonyl-containing anions and [Ph4P]þ cations. The crystal structure features

linear polymeric chains of anions whereby adjacent hexaruthenium carbonyl

clusters are linkedby tetra-coordinatedAgþ cations.Associatedwith every sec-

ond cluster is a [Ph4P]þ cation via a singleM–CO(lone pair). . .p(arene) inter-

action, as illustrated in Fig. 2.11; see Table 2.9 for geometric parameters.

P

OO

O

O

O

OOO

OO

O

O

O

O

Ag

RuRu

Ru

RuRuRu

OO

Figure 2.11 One-dimensional motif J: polymeric chain in 84121 with every secondrepeat unit connected to a counter ion by one M–CO(lone pair). . .p(arene) interaction.

Table 2.9 Geometric data characterizing M–CO(lone pair). . .p(arene) interactions inone-dimensional motif J: polymeric chain associated with counter cation via oneinteraction per every second repeat unit, and three-dimensional motif KCompound/Reference d (Å) a (�) b (�) Metal

Motif J

84 (121) 3.20 4.6 162.2 Ru

Motif K

85 (122) 3.49 7.3 169.2 Re


3.8. Motif KMotif K, the last of 11 motifs, is adopted by a sole example and is the stand-

out motif in that unlike zero-dimensional motifsA–D and one-dimensional

motifs E–J, the M–CO(lone pair). . .p(arene) interactions stabilize a three-dimensional architecture. MotifK is found in the crystal structure of 85,122 a

portion of which is illustrated in Fig. 2.12; see Table 2.9 for geometric pa-

rameters. Each molecule of 85 participates in two acceptor and two donor

contacts but these connect to four different molecules.

Figure 2.12 Three-dimensional motif H in 85122 sustained by two M–CO(lone pair). . .p(arene) interactions per molecule.


4. THIO- AND SELENOCARBONYL ANALOGUES

Compared to the ubiquitous carbonyls, thiocarbonyl analogues are

comparatively rare and selenocarbonyls are virtually nonexistent. Of the

22 thiocarbonyl structures satisfying the search criteria illustrated in Fig. 2.1,

in only 86123 were M–CS(lone pair). . .p(arene) interactions observed. Theresulting supramolecular architecture, a zigzag chain sustained by a single

M–CS(lone pair). . .p(arene) interaction per molecule, that is, analogous

to motifG, is shown in Fig. 2.13. Interestingly, the molecule of 86 also con-

tains carbonyl ligands but it is the thiocarbonyl ligand that forms the M–CS

(lone pair). . .p(arene) interaction. No evidence was found for M–CSe(lone

pair). . .p(arene) interactions.


Figure 2.13 Zigzag supramolecular chain in 86123 sustained by a single M–CS(lonepair). . .p(arene) interactions per molecule.

5. STRENGTH AND CORRELATIONS

By their very nature, the described M–CO(lone pair). . .p(arene) inter-
actions are weak. As a guide to their strength, a range of energies of stabiliza-
tion of related O(lone pair). . .p(aryl) interactions has been estimated to be

1.5–5.1 kJ mol�1.11a,34 As such, well-defined geometric correlations are

not anticipated.21,124 Indeed, plots of d, a, and b, in all possible

combinations, do not reveal any systematic correlations. This is expected,

given the wide range of chemical compositions of the structures surveyed,

in terms of the nature of the transition metal, the nuclearity of the species,

the charge, and, not to mention, the diversity in the additional ligand

molecules. The above notwithstanding, it is salutatory to mention that

often the presence of M–CO(lone pair). . .p(arene) interactions is indicatedin automatic structure analysis programs such as PLATON.39c

Among the structures 1–85 surveyed here, it is noted that four pairs,

that is, 7 (Ir)46 and 8 (Rh),47 39 (W)78 and 40 (Cr),78 56 (Re)94 and 57


(Mn),95 and 59 (Os)97 and 61 (Ru),97 are isostructural, differing only in

the nature of the metal centers which, in each case, belongs to the same

group of the periodic table. It is noted that for each pair, the shortest d

associated with the M–CO(lone pair). . .p(arene) interaction involved

the heavier element. The differences in d are small and the apparent trend

might be fortuitous. If a trend does exist in the aforementioned iso-

structural series, no trends are evident when considering heterometallic

structures.

Several species engaged in M–CO(lone pair). . .p(arene) interactions areheterometallic in which different metal centers carry carbonyl ligands. The

structures 10 (Fe*, Co), 27 (Ru*, Ir), 28 (Fe, Co*), 32 (W*, Re), 36 (Ni,

Ru*), 67 (Mo, Re*), and 75 (Ru*, Pt) present no indications for preferen-

tial engagement of a metal center over another, for example, first versus sec-

ond row, second versus third row, low group number versus higher group

number; elements indicated with an asterisk are involved in theM–CO(lone

pair). . .p(arene) interaction.

6. CONCLUSIONS AND OUTLOOK

The foregoing discussion plainly indicates that M–CO(lone pair). . .
p(arene) interactions do exist in the structures of a number of
transitionorganometal carbonyl derivatives.At aminimum,molecules aggre-

gate to form dimeric supermolecules. In over 40% of the cases, the molecules

self-assemble into one-dimensional supramolecular chains of varying topol-

ogy. There was only one case where a three-dimensional architecture was

found to be stabilized by M–CO(lone pair). . .p(arene) interactions. In spite

of their inherent weak nature, M–CO(lone pair). . .p(arene) interactions doprovide a measure of stability to their crystal structures and lead to well-

defined supramolecular architectures. Such interactions ought to be searched

for when analyzing crystal structures of transition organometal carbonyl

derivatives in order to have a complete understanding of the way molecules

associate in the solid state.

ACKNOWLEDGMENTSJ. Z.-S. thanks the Brazilian agencies FAPESP, CNPq (306532/2009-3), and CAPES (808/

2009) for financial support. The Ministry of Higher Education (Malaysia) is thanked for

funding crystal engineering studies through the High-Impact Research scheme (UM.C/

HIR-MOHE/SC/12).


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