www.sciencemag.org/cgi/content/full/316/5824/585/DC1

Supporting Online Material for

A Dinuclear Ni(μ-H)Ru Complex Derived from H2

Seiji Ogo,* Ryota Kabe, Keiji Uehara, Bunsho Kure, Takashi Nishimura, Saija C. Menon, Ryosuke Harada, Shunichi Fukuzumi, Yoshiki Higuchi, Takashi Ohhara,

Taro Tamada, Ryota Kuroki

*To whom correspondence should be addressed. E-mail: ogo-tcm@mbox.nc.kyushu-u.ac.jp

Published 27 April, Science 316, 585 (2007)

DOI: 10.1126/science.1138751

This PDF file includes:

Materials and Methods Figs. S1 to S18 Tables S1 and S2 References

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A Table of Contents

Experimental Methods page 3

Table S1, crystal data for [1](OTf)2 and [2](NO3) page 6

Table S2, selected bond lengths and angles for [1](OTf)2 and [2](NO3) page 7

Fig. S1, NMR spectrum of [1](SO4) page 8

Fig. S2, NMR spectrum of [1](OTf)2 page 9

Fig. S3, NMR spectrum of [1](NO3)2 page 10

Fig. S4, IR spectrum of [1](OTf)2 page 11

Fig. S5, ESI mass spectra of [1](SO4) page 12

Fig. S6, ESI mass spectra of [1](OTf)2 page 13

Fig. S7, ESI mass spectra of [1](NO3)2 page 14

Fig. S8, XPS spectra of [1](OTf)2 and [2](NO3) page 15

Fig. S9, Magnetic susceptibility measurements of [1](OTf)2 and [2](NO3) page 16

Fig. S10, ORTEP drawing of [1](OTf)2 by X-ray analysis page 17

Fig. S11, Synthetic chart of [1]2+ and [2]+ from [3]2+ in water page 18

Fig. S12, IR spectra of [2](NO3) page 19

Fig. S13, ESI mass spectra of [2](NO3) page 20

Fig. S14, NMR spectra of [2](NO3) page 21

Fig. S15, ESR spectrum of [2](NO3) page 22

Fig. S16, ORTEP drawing of [2](NO3) by X-ray analysis page 23

Fig. S17, Fo-Fc map of [2](NO3) by neutron diffraction analysis page 24

Fig. S18, ESI mass spectra of [2](NO3) page 25

References page 26

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Experimental Section

Materials and Methods. All experiments were carried out under Ar atmosphere by using

standard Schlenck techniques or a glovebox. The manipulations in the acidic media were carried out

with plastic and glass apparatus (without metal components). Distilled water, 0.1 M NaOH/H2O, and

0.1 M HNO3/H2O were purchased from Wako Pure Chemical Industries, Ltd., 65% DNO3/D2O (99%

D) from Isotec Inc., D2O (99.9% D) from Cambridge Isotope Laboratories, Inc., H2 gas (> 99.9999%)

from Taiyo Toyo Sanso Co., Ltd. and D2 gas (> 99.5%) from Sumitomo Seika Chemicals Co., Ltd.

The ruthenium aqua complex [Ru(η6-C6Me6)(H2O)3](SO4) {[3](SO4)} and nickel complex [NiIIL] {4,

L = N,N’-dimethyl-N,N’-bis(2-mercaptoethyl)-1,3-propanediamine} were prepared by the methods

described in the literature (18, 19). 1H NMR spectra were recorded on a Bruker Avance500 or a JEOL JNM-AL300 spectrometer at

25˚C. Chemical shifts were referenced to the 3-(trimethylsilyl)propionic-2,2,3,3-d4 acid sodium salt

(TSP). ESI-MS data were obtained by an API 365 triple-quadrupole mass spectrometer (PE-Sciex) in

the positive detection mode, equipped with an ion spray interface. The sprayer was held at a potential

of + 5.0 kV, and compressed N2 was employed to assist liquid nebulization. IR spectra were recorded

on a Thermo Nicolet NEXUS 870 FT-IR instrument using 2 cm-1 standard resolution at ambient

temperature. X-band ESR spectra were measured at 10 K by using a Bruker EMX plus spectrometer.

The magnetic susceptibility measurements were performed at 300 K using a Quantum Design

MPMS-5 SQUID magnetometer. X-ray photoelectron spectra (XPS) were measured on a VG

Scientific ESCALAB MK II electron spectrometer by use of Mg-Kα radiation, and the binding

energies were corrected by assuming C 1s binding energy of the carbon atoms of the ligand in

specimens as 284.5 eV (S1).

pH-Adjustment. In a pH range of 3.0–10.0, the pH values of the solutions were determined by a

pH meter (TOA; HM25G) equipped with a pH combination electrode (TOA, GST-5725C) and a pH

meter (IQ Scientific Instruments, Inc., IQ200) equipped with a stainless steel-micro pH probe (IQ

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Scientific Instruments, Inc., PH15-SS). Values of pD were corrected by adding 0.4 to the observed

values {pD = pH meter reading + 0.4} (S2, S3).

[(NiIIL)RuII(η6-C6Me6)(H2O)](SO4) {[1](SO4)}. A solution of a water-soluble ruthenium aqua

complex [3](SO4) (256 mg, 0.6 mmol) in 40 mL H2O was added to a solution of a nickel complex 4

(167 mg, 0.6 mmol) in 40 mL H2O. The solution was stirred at 25ºC. After 2 h, the solvent was

evaporated to yield a red hygroscopic powder of [1](SO4), which was dried in vacuo {70% isolated

yield based on [4]. 1H NMR (500 MHz, in D2O, reference to TSP, pD 7.7, 25˚C): δ 2.22 {s, 18H,

C6(CH3)6}, 2.68 (s, 6H, N-CH3), 1.67-1.89, 2.09-2.48, 2.62-2.84, and 3.16-3.25 (m, 14H, -CH2-).

[(NiIIL)RuII(η6-C6Me6)(H2O)](NO3)2 {[1](NO3)2}. A solution of [1](SO4) (100 mg, 0.15 mmol)

in 50 mL H2O was loaded onto a QAE-Sephadex A-25 column (NO3- form) and eluted with water.

The elute was evaporated to give a red hygroscopic powder of [1](NO3), which was dried in vacuo

{78% isolated yield based on [1](SO4)}. 1H NMR (500 MHz, in D2O, reference to TSP, pD 7.0,

25˚C): δ 2.18 {s, 18H, C6(CH3)6}, 2.65 (s, 6H, N-CH3), 1.68-1.87, 2.08-2.45, 2.58-2.81, and 3.14-3.20

(m, 14H, -CH2-).

[(NiIIL)RuII(η6-C6Me6)(H2O)](OTf)2 {[1](OTf)2, OTf = CF3SO3-}. The aqueous solution of

NaOTf (172 mg 1.0 mmol) in 1 mL H2O was added to the aqueous solution of aqua complex

[1](SO4) (684 mg, 1.0 mmol) in 10 mL H2O. After brown oil was filtered out, NaOTf (1.72 g 10

mmol) was added to the resulting solution to give a red microcrystalline of [1](OTf)2, which was dried

in vacuo {26% isolated yield based on [1](SO4)}. 1H NMR (500 MHz, in D2O, reference to TSP, pD

6.6, 25˚C): δ 2.15 {s, 18H, C6(CH3)6}, 2.62 (s, 6H, N-CH3), 1.64-1.84, 2.04-2.42, 2.53-2.78, and

3.10-3.18 (m, 14H, -CH2-). Anal. Calcd for [1](OTf)2: C23H40F6N2NiO7RuS4·3H2O: C, 30.27; H, 5.08;

N, 3.07. Found: C, 30.35; H, 5.06; N, 3.21.

[(NiIIL)(H2O)(µ-H)RuII(η6-C6Me6)](NO3) {[2](NO3)}. The aqua complex [1](NO3)2 (125 mg,

0.2 mmol) was added to phosphate buffer solution (5 mL) of pH 6.8. H2 (0.1 MPa) was bubbled

through the solution at 25ºC to gradually precipitate dark-red crystals of [2](NO3). After 3 h of the H2

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bubbling, the crystals were isolated by filtration {34% isolated yield based on [1](NO3)2}. ESI-MS

analysis of the filtrate has shown a prominent signal at m/z 543.2 {relative intensity (I) =100% in the

range of m/z 200-1000}, that corresponds to [2 - H2O]+. ESI-MS (in H2O), m/z 543.2 ([2 – H2O]+; I =

100% in the range of m/z 100-2000). IR (cm-1) 1740 (νNi-H-Ru). Anal. Calcd for [2](NO3)·H2O:

C21H43N3NiO5RuS2: C, 39.32; H, 6.76; N, 6.55. Found: C, 39.54 H, 6.62; N, 6.54.

X-ray Crystallographic Analysis. Dark-red crystals of [1](OTf)2 used in X-ray analysis were

obtained from an aqueous solution of [1](OTf)2. Dark-red crystals of [2](NO3) were obtained from an

aqueous solution of [2](NO3). Measurements were made on a Rigaku/MSC Mercury CCD

diffractometer with graphite monochromated Mo-Kα radiation (λ = 0.7107). All calculations were

performed using the teXsan crystallographic software package of Molecular Structure Corporation.

Neutron Crystallographic Analysis. Measurement of dark-red crystal of [2](NO3) was made on

the BIX-3 single crystal neutron diffractometer at JAEA (λ = 1.5100) (S4) at room temperature.

Crystal size was 3.0 × 2.0 × 0.2 mm and measurement time was 8 days. 10161 reflections were

observed and 3858 were unique. A numerical absorption correction was done by program ABSG in

PLATON (S5). In structure refinement, the positions of hydrogen atoms were determined from

differential Fourier map and those of all atoms except a nitrate ion and a solvent water were refined

independently. A nitrate ion and solvent water were refined with rigid model. Displacement

parameters of all atoms were refined with an anisotropic model, except for S1, S2, H8C, H20A,

H21A, H21B, O5, HO5A, and HO5B which were treated isotropically. All calculations were

performed using SHELXL-97 (S6), and computation of molecular graphics was performed with

MIFit (S7), and ORTEP-3 for Windows (S8).

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Table S1. Crystal Data, Details of Intensity Measurements, and Structure Refinements for [1](OTf)2 and [2](NO3)

X-ray, [1](OTf)2 neutron, [2](NO3) X-ray, [2](NO3) empirical formula C23H46F6N2NiO10RuS4 C21H42N3NiO4.5RuS2 C21H42N3NiO4.5RuS2 fw 912.62 632.47 632.47 crystal system orthorhombic monoclinic monoclinic space group (number) Pca21 (#29) P21/a (#14) P21/a (#14) cell dimensions a, Å 23.544(1) 15.141(1) 15.127(6) b, Å 8.9842(4) 11.944(1) 11.926(5) c, Å 17.3218(9) 14.890(1) 14.757(6) α, deg 90.000 90.000 90.000 β, deg 90.000 105.272(2) 104.487(4) γ, deg 90.000 90.000 90.000 V, Å3 3663.9(3) 2597.7(3) 2577(1) T, K 173 293 173 Z 4 4 4 dcalcd, g cm-3 1.654 1.617 1.630 µ, cm-1 12.34 5.63 15.13 radiation (λ, Å) MoKα (0.7107) neutron (1.5100) MoKα (0.7107) 2θ range, deg 7.0 – 55.0 6.0 – 140.6 6.6 – 55.0 crystal size, mm 0.25 × 0.25 × 0.15 3.0 × 2.0 × 0.2 0.30 × 0.10 × 0.05 no. of reflns measd 29598 10161 20819 no. of unique reflns 8085 3858 5892 no. of variable parameters 469 635 302 aR (for F2 > 2σ(F2)) 0.042 0.162 0.048 aR (for all reflections) 0.052 0.172 0.089 bwR (for all reflections) 0.106 0.362 0.109 cgoodness of fit, S 1.00 0.97 1.00

aR = Σ||Fo| – |Fc|| / Σ|Fo|. bwR = [Σw(Fo

2 – Fc2)2 / Σw(Fo

2)2]1/2. cS = [Σ[w(Fo

2 – Fc2)2] / (Nref – Nparam)]1/2.

Nref = the number of reflections used in the refinement, Nparam = the number of refined parameters.

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Table S2. Selected Bond Lengths (Å) and Angles (deg) for [1](OTf)2 and [2](NO3)

X-ray, [1](OTf)2 neutron, [2](NO3) X-ray, [2](NO3) Ni1–Ru1 3.1611(6) 2.739(3) 2.7372(7) Ni1-H1 - 1.859(7) 1.88(5) Ni1–O1 - 2.122(5) 2.100(3) Ni1–S1 2.165(1) 2.359(10) 2.359(1) Ni1–S2 2.165(1) 2.362(9) 2.367(1) Ni1–N1 1.963(4) 2.119(3) 2.127(4) Ni1–N2 1.974(4) 2.117(4) 2.127(4) Ru1–H1 - 1.676(8) 1.61(6) Ru1–O1 2.154(3) - - Ru1–S1 2.427(1) 2.375(11) 2.401(1) Ru1–S2 2.411(1) 2.388(7) 2.412(1) Ru1–C10 2.209(5) 2.229(5) 2.207(5) Ru1–C11 2.213(5) 2.219(5) 2.235(5) Ru1–C12 2.213(5) 2.209(4) 2.232(5) Ru1–C13 2.200(5) 2.261(4) 2.252(5) Ru1–C14 2.162(5) 2.227(4) 2.230(5) Ru1–C15 2.218(5) 2.222(4) 2.216(5) Ni1–H1–Ru1 - 101.47(43) 102(2) Ni1–S1–Ru1 86.81(4) 70.7(3) 70.21(4) Ni1–S2–Ru1 87.20(5) 70.4(2) 69.89(4) H1–Ni1–O1 - 177.7(3) 178(1) H1–Ni1–S1 - 81.3(4) 79(1) H1–Ni1–S2 - 82.4(3) 81(1) S1–Ni1–S2 80.99(6) 77.8(3) 80.20(5) H1–Ru1–S1 - 84.5(4) 83(1) H1–Ru1–S2 - 85.4(3) 85(1) O1–Ru1–S1 86.20(9) - - O1–Ru1–S2 90.35(9) - - S1–Ru1–S2 71.07(4) 77.0(3) 78.47(4)

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6 5 4 3 2 1

ppm

0

C6(CH3)6TSP

water

N-CH3CH2

Fig. S1. 1H NMR spectrum of [1](SO4) in D2O at pD 7.7 at 25˚C.

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6 5 4 3 2 1

ppm

0

C6(CH3)6

TSP

water

N-CH3

CH2

Fig. S2. 1H NMR spectrum of [1](OTf)2 in D2O at pD 6.6 at 25˚C.

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6 5 4 3 2 1

ppm

0

C6(CH3)6

TSPwater

N-CH3CH2

Fig. S3. 1H NMR spectrum of [1](NO3)2 in D2O at pD 7.0 at 25˚C.

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2000 1800 1600 1400 1200

Wavenumber / cm-1

1000

Fig. S4. IR spectrum of [1](OTf)2 as a KBr disk.

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271.0

559.2

200 400 600 800 1000

m/z

560 565 570550 555

m/z

559.2A B

C

Fig. S5. (A) Positive-ion ESI mass spectrum of [1](SO4) in H2O. The signal at m/z 271.0 corresponds to [1 – H2O]2+. (B) The signal at m/z 559.2 corresponds to [1 – H]+. (C) Calculated isotopic distribution for [1 – H]+.

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271.0

691.0

680 685 690 695 700 705

m/z

200 400 600 800 1000

m/z

691.0A B

C

Fig. S6. (A) Positive-ion ESI mass spectrum of [1](OTf)2 in H2O. The signal at m/z 271.0 corresponds to [1 – H2O]2+. (B) The signal at m/z 691.0 corresponds to [1 – H2O + OTf]+. (C) Calculated isotopic distribution for [1 – H2O + OTf]+.

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271.0

559.2

200 400 600 800 1000

m/z

560 565 570550 555

m/z

559.2A B

C

Fig. S7. (A) Positive-ion ESI mass spectrum of [1](NO3)2 in H2O. The signal at m/z 271.0 corresponds to [1 – H2O]2+. (B) Signal at m/z 559.2 for [1 – H]+. (C) Calculated isotopic distribution for [1 – H]+.

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Ni 2p3/2

880910 900 890

Binding Energy / eV

[1](OTf)2

[2](NO3)

A

B

275290 280285

Binding Energy / eV

270

C 1s

Ru 3d5/2

[1](OTf)2

[2](NO3)

C

D

Fig. S8. (A) XPS of Ni 2p region for [1](OTf)2 at 300 K. (B) XPS of Ni 2p region for [2](NO3) at 300 K. (C) XPS of Ru 3d region for [1](OTf)2 at 300 K. (D) XPS of Ru 3d region for [2](NO3) at 300 K.

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1.0 2.0 3.0 4.0 5.00

10

0

-10

-20

-30

-40

A

M / e

mu

Oe

-1 m

ol-1

H / 104 Oe

80

60

40

20

0

-20

B

M / e

mu

Oe

-1 m

ol-1

1.0 2.0 3.0 4.0 5.00

H / 104 Oe

Fig. S9. (A) M versus H plot of [1](OTf)2 at 300 K. (B) M versus H plot of [2](NO3) at 300 K.

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O1

S1

S2

Ni1Ru1

N2

N1

Fig. S10. ORTEP drawing of [1](OTf)2 determined by X-ray analysis. The counter anion (OTf) and the solvent are omitted for clarity.

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[1](SO4)[1](OTf)2 [1](NO3)2

[2](NO3)

red crystals suitable forX-ray analysis

dark-red crystals suitable for neutron diffraction and

X-ray analysis

NaOTf

H2

hygroscopic red powder

hygroscopic red powder

[3](SO4)

[NiL] (4)

microcrystalline(starting material)

QAE-Sephadex A-25

column (NO3- form)(OTf = CF3SO3

-)

H2H2

[2](OTf) oil

microcrystalline

Fig. S11. Synthetic chart of [1]2+ and [2]+ from [3]2+ in water.

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2000 1800 1600 1400 1200

Wavenumber / cm-1

1000

1740 1248

A

B

Fig. S12. IR spectra as KBr disks of [2](NO3) (A) and [D-labeled 2](NO3) (B).

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200 400 600 800 1000

m/z

540 545 550530 535

m/z

543.2543.2

555

A B

C

200 400 600 800 1000

m/z

540 545 550530 535

m/z

544.2544.2

555

D E

F

Fig. S13. (A) Positive-ion ESI mass spectrum of [2](NO3) in H2O. (B) Signal at m/z 543.2 for [2 - H2O]+. (C) Calculated isotopic distribution for [2 - H2O]+. (D) Positive-ion ESI mass spectrum of [D-labeled 2](NO3) in D2O. (E) The signal at m/z 544.2 for [D-labeled 2 - D2O]+. (F) Calculated isotopic distribution for [D-labeled 2 - D2O]+.

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150 100 50ppm

0 -50

150 100 50ppm

0 -50

A

B

Fig. S14. 1H NMR spectra of [2](NO3) in H2O at 25 ºC (A) and [D-labeled 2](NO3) in D2O at 25 ºC (B).

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400100 200 300

mT Fig. S15. ESR spectrum of [2](NO3) in H2O at 10 K.

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S1

Ni1

H1

Ru1S2

N2

N1

O1

Fig. S16. ORTEP drawing of [2](NO3) determined by X-ray analysis. The counter anion (NO3) and the solvent are omitted for clarity.

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A

NiN

N

O

S

S

Ru

B

C

Fig. S17. (A) Fo-Fc map around the core structure of [2](NO3) calculated from the neutron diffraction data. The H1 atom was omitted in the Fc calculation. The pink, red and light blue mesh shows –3σ, –6σ and +3σ contour, respectively. (B) Fo map at –2σ. (C) Fo map at +3σ.

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200 400 600 800 1000

m/z

540 545 550530 535

m/z

543.2

543.2

555

A B

C

200 400 600 800 1000

m/z

540 545 550530 535

m/z

544.2

544.2

555

D E

F

Fig. S18. (A) Positive-ion ESI mass spectrum of [2](NO3) synthesized from [1](NO3)2 with H2 in D2O. (B) Signal at m/z 543.2 for [2 - D2O]+. (C) Calculated isotopic distribution for [2 - D2O]+. (D) Positive-ion ESI mass spectrum of [D-labeled 2](NO3) synthesized from [1](NO3)2 with D2 in H2O. (E) The signal at m/z 544.2 for [D-labeled 2 - H2O]+. (F) Calculated isotopic distribution for [D-labeled 2 - H2O]+.

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References

S1. J. F. Moulder, W. F. Stiekle, P. E. Sobol, K. D. Bomben, Handbook of X-ray

Photoelectron Spectroscopy (Physical Electronics, Inc., Minnesota, 1995).

S2. P. K. Glasoe, F. A. Long, J. Phys. Chem. 64, 188 (1960).

S3. K. Mikkelsen, S. O. Nielsen, J. Phys. Chem. 64, 632 (1960).

S4. I. Tanaka, K. Kurihara, T. Chatake, N. Niimura, J. Appl. Cryst. 35, 34 (2002).

S5. A. L. Spek, J. Appl. Cryst. 36, 7 (2003).

S6. G. M. Sheldrick, SHELXL-97, University of Göttingen, Germany (1997).

S7. D. E. McRee and J. Badger, MIFit, Rigaku (2003).

S8. L. J. Farrugia, J. Appl. Cryst. 30, 565 (1997).