Polymeric Alkylidene-Bridged Platinum Complex [{Pt2(-Cl)2{-C(OBu)Me}2}n]: Synthesis, Reactivity, and Quantum Chemical Calculations

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• 作者：Christian Albrecht ; Sebastian Schwieger ; Tobias R&uuml ; ffer ; Clemens Bruhn ; Tadeusz Lis ; Dirk Steinborn
• 刊名：Organometallics
• 出版年：2007
• 出版时间：November 19, 2007
• 年：2007
• 卷：26
• 期：24
• 页码：6000 - 6008
• 全文大小：236K
• 年卷期：v.26,no.24(November 19, 2007)
• ISSN：1520-6041

文摘

H₂[PtCl₆]·6H₂O in dried n-BuOH was found to react with an excess of bis(trimethylsilyl)acetylene(BTMSA), yielding the polymeric alkylidene-bridged platinum complex [{Pt₂(-Cl)₂{-C(OBu)Me}₂}_n](3). Reactions of complex 3 with monodentate N, P, and S donors afforded dinuclear alkylidene-bridgedcomplexes trans-[{PtCl(L)}₂{-C(OBu)Me}₂] (2-Mepy, 5a; 4-Mepy, 5b; 2-Brpy, 5c; PPh₃, 6a; PPh₂(4-py), 6b; tht, 7) (tht = tetrahydrothiophene) in yields between 51 and 92%. Owing to a syn and antiarrangement of the butoxy substituents, complexes 5-7 were obtained as diastereomeric mixtures. Allcomlexes were characterized by means of microanalysis and IR and NMR spectroscopy. Furthermore,X-ray diffraction analyses were performed for the complexes 5a-c and 6a,b, exhibiting central Pt₂C₂rings with Pt-Pt distances between 2.573(1) and 2.681(1) Å. Quantum chemical studies of 6a using theAIM theory gave evidence of the bonding in the Pt₂C₂ moiety in terms of four-centered bonds.