Metal-Metal Interactions in Dinuclear d8 Metal Cyanide Complexes Supported by Phosphine Ligands. Spectroscopic Properties and ab Initio Calculations of [M2(
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- 作者：Bao-Hui Xia ; Chi-Ming Che ; David Lee Phillips ; King-Hung Leung ; and Kung-Kai Cheung
- 刊名：Inorganic Chemistry
- 出版年：2002
- 出版时间：July 29, 2002
- 年：2002
- 卷：41
- 期：15
- 页码：3866 - 3875
- 全文大小：142K
- 年卷期：v.41,no.15(July 29, 2002)
- ISSN：1520-510X
文摘
Structural, spectroscopic properties on the dinuclear [M2(dcpm)2(CN)4] (M = Pt, 1a; Ni, 2a, dcpm =bis(dicyclohexylphosphino)methane) and [M2(dmpm)2(CN)4] (M = Pt, 1b; Ni, 2b, dmpm = bis(dimethylphosphino)methane) and the mononuclear trans-[M(PCy3)2(CN)2] (M = Pt, 3; Ni, 4, PCy3 = tricyclohexylphosphine) andtheoretical investigations on the corresponding model compounds are described. X-ray structural analyses revealPt···Pt and Ni···Ni distances of 3.0565(4)/3.189(1) Å and 2.957(1)/3.209(8) Å for 1a/1b and 2a/2b, respectively.The UV-vis absorption bands at 337 nm (
2.41 × 104 dm3 mol-1 cm-1) for 1a and 328 nm ( 2.43 × 104 dm3mol-1 cm-1) for 1b in CH2Cl2 are assigned to 1(5d
* 
6p) electronic transitions originating from Pt(II)-Pt(II)interactions. Resonance Raman spectroscopy of 1a, in which all the Raman intensity appears in the Pt-Pt stretchfundamental (93 cm-1) and overtone bands, verifies this metal-metal interaction. Complexes 1a and 1b exhibitphotoluminescence in the solid state and solution. For the dinuclear nickel(II) complexes 2a and 2b, neitherspectroscopic data nor theoretical calculation suggests the presence of Ni(II)-Ni(II) interactions. The intense absorptionbands at 
> 320 nm in the UV-vis spectra of 2a and 2b are tentatively assigned to d d transitions.
2.41 × 104 dm3 mol-1 cm-1) for 1a and 328 nm ( 2.43 × 104 dm3mol-1 cm-1) for 1b in CH2Cl2 are assigned to 1(5d* 6p) electronic transitions originating from Pt(II)-Pt(II)interactions. Resonance Raman spectroscopy of 1a, in which all the Raman intensity appears in the Pt-Pt stretchfundamental (93 cm-1) and overtone bands, verifies this metal-metal interaction. Complexes 1a and 1b exhibitphotoluminescence in the solid state and solution. For the dinuclear nickel(II) complexes 2a and 2b, neitherspectroscopic data nor theoretical calculation suggests the presence of Ni(II)-Ni(II) interactions. The intense absorptionbands at > 320 nm in the UV-vis spectra of 2a and 2b are tentatively assigned to d d transitions.