| Abstrakt: |
Six novel Pt–Rh dinuclear complexes (1–6), [PtRh(PVM)2(NH3)2Cl3]·4H2O (1, PVM = tBuCONH–), [PtRh(PVM)2(en)Cl3]·3H2O (2, en = ethylenediamine), [PtRh(PVM)2(NH2CH3)2Cl3]·3H2O (3), [PtRh(PVM)2(NH2tBu)2Cl3]·3H2O (4), [PtRh(TCM)2(NH3)2Cl3] (5, TCM = Cl3CCONH–), and [PtRh(BZM)2(NH3)2Cl3]·H2O (6, BZM = PhCONH–), have been synthesized from Pt mononuclear complexes having nitrogen-coordinated amidate ligands with noncoordinated amidate oxygen atoms. X-ray analysis revealed that compounds 1 and 2 form zigzag one-dimensional chains in the form [–Pt–Rh–Cl–]n. The oxidation states of the metal ions have been determined by X-ray photoelectron spectroscopy (XPS) and 195Pt NMR spectroscopic analysis, and are Pt(+2, d8)···Rh(+3, d6). In comparison with the Pt–Rh distances found in the literature, it has become apparent that the Pt–Rh dinuclear complexes have a dative Pt(d8)→Rh(d6) bond, where the Pt dz2 orbital is stabilized by the overlap with the dz2 orbital of the Rh atom. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007) |
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