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[Ph4P]2 [Sb2 I8]: Weak Interactions between Phenyl Groups of the Cation and Antimony Atoms of the Anion

✍ Scribed by Prof. Dr. Siegfried Pohl; Wolfgang Saak; Detlev Haase


Publisher
John Wiley and Sons
Year
1987
Tongue
English
Weight
280 KB
Volume
26
Category
Article
ISSN
0044-8249

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✦ Synopsis


formula 5a.Ii'] Its binuclear constitution follows from the diamagnetism, which requires a direct metal-metal interaction, and from the reaction with trimethylphosphane leading to formation of the paramagnetic Re'" complex 6a.[143 Taking into consideration the liberation of ethylenel ethane and I-butene/n-butane, respectively (detected by gas chromatography), the formation of 5a, which involves reduction (ReV-ReSV), may be explained by a p-hydride shift and its consequences (Scheme 2): the alkyl intermediate A rearranges to give the hydrido(o1efin) isomer B, which then undergoes reductive decomposition with olefin elimination and intermolecular alkane formation; elemental hydrogen does not appear during the formation of 5a. These findings show that alkyltin compounds of highervalent metal halide systems, although alkylating initially in a redox-neutral reaction, can subsequently lead to reduction of the transition metal when, sterically and electronically (Lewis acids), the metal allows alkyl rearrangement processes such as the p-hydride shift to occur. It is interesting that even an excess of Sn(CH3), does not lead to multiple methylation of the tetrachloro complexes l a , b ; the compound [(q5-CsMes)Re(CH,),] is obtainable, however, from la via the Grignard route.[i5'

CH,

  • A