| 12926961 |
Xia BH, Zhang HX, Che CM, Leung KH, Phillips DL, Zhu N, Zhou ZY: Metal-metal interactions in heterobimetallic d8-d10 complexes. J Am Chem Soc. 2003 Aug 27;125(34):10362-74.
Structures and spectroscopic investigation of [M'M' '(mu-dcpm) 2 (CN) 2]+ (M' = Pt, Pd; M' ' = Cu, Ag, Au) and related complexes by UV-vis absorption and resonance Raman spectroscopy and ab initio calculations.. X-ray structural and spectroscopic properties of a series of heterodinuclear d (8)-d (10) metal complexes [M'M' '(mu-dcpm)(2)(CN)(2)](+) containing d (8) Pt (II), Pd (II), or Ni (II) and d (10) Au (I), Ag (I), or Cu (I) ions with a dcpm bridging ligand have been studied (dcpm = bis (dicyclohexylphosphino) methane; M' = Pt, M' ' = Au 4, Ag 5, Cu, 6; M' ' = Au, M' = Pd 7, Ni 8). X-ray crystal analyses showed that the metal...metal distances in these heteronuclear metal complexes are shorter than the sum of van der Waals radii of the M' and M' ' atoms. The UV-vis absorption spectra of 4-6 display red-shifted intense absorption bands from the absorption spectra of the mononuclear trans-[Pt (phosphine)(2)(CN)(2)] and [M' '(phosphine)(2)](+) counterparts, attributable to metal-metal interactions. The resonance Raman spectra confirmed assignments of (1)[nd (sigma)-->(n + 1) p (sigma)] electronic transitions to the absorption bands at 317 and 331 nm in 4 and 6, respectively. The results of theoretical calculations at the MP2 level reveal an attractive interaction energy curve for the skewed [trans-Pt (PH (3))(2)(CN)(2)-Au (PH (3))(2)(+)] dimer. The interaction energy of Pt (II)-Au (I) was calculated to be ca. 0.45 ev. |
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