Synthesis, Crystal Structures, and Oxidation States of MM′X-Type Platinum–Rhodium Dinuclear Complexes Having Amidate Bridging Ligands
✍ Scribed by Kazuhiro Uemura; Kana Yamasaki; Kôichi Fukui; Kazuko Matsumoto
- Publisher
- John Wiley and Sons
- Year
- 2007
- Tongue
- English
- Weight
- 276 KB
- Volume
- 2007
- Category
- Article
- ISSN
- 1434-1948
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✦ Synopsis
Abstract
Six novel Pt–Rh dinuclear complexes (1–6), [PtRh(PVM)~2~(NH~3~)~2~Cl~3~]·4H~2~O (1, PVM = t__BuCONH^–^), [PtRh(PVM)~2~(en)Cl~3~]·3H~2~O (2, en = ethylenediamine), [PtRh(PVM)~2~(NH~2~CH~3~)~2~Cl~3~]·3H~2~O (3), [PtRh(PVM)~2~(NH~2~t__Bu)~2~Cl~3~]·3H~2~O (4), [PtRh(TCM)~2~(NH~3~)~2~Cl~3~] (5, TCM = Cl~3~CCONH^–^), and [PtRh(BZM)~2~(NH~3~)~2~Cl~3~]·H~2~O (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 ^195^Pt NMR spectroscopic analysis, and are Pt(+2, d^8^)···Rh(+3, d^6^). 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(d^8^)→Rh(d^6^) bond, where the Pt d orbital is stabilized by the overlap with the d orbital of the Rh atom. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)