Supporting Online Material for - Experimental Section Materials and Methods. All experiments were...

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  • 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

  • 2/26

    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

  • 5/26

    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