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Communication | Special issue | Vol 79, No. 1, 2009, pp.311-318
Published online, 21st August, 2008
DOI: 10.3987/COM-08-S(D)5
Intramolecular Si-C and C-H Bond Activation in a Platinum Complex Leading to the Formation of the Platinacycles

Norihiro Tokitoh,* Masahiro Kawai, Nobuhiro Takeda, and Takahiro Sasamori

*Institute for Chemical Research, Kyoto University, Gokasho, Uji, Kyoto 611-0011, Japan


Reduction of dichloroplatinum complex dl-1 bearing two bulky aromatic substituents, Bbt groups (2,6-bis[bis(trimethylsilyl)methyl]-4-[tris(trimethylsilyl)methyl]phenyl), by sodium metal gave a unique platinacycle 2, a hydridoplatinum complex of [PtH{CH2SiMe2CH(SiMe3)C6H2-3-CH(SiMe3)2-5-C(SiMe3)3-2-P(Me)CH2CH2 (Me)PBbt}], which seems to be most likely formed via the initial formation of the corresponding Pt(0) complex and the subsequent intramolecular insertion of the Pt(0) center to the H-CH2 bond of the o-bis(trimethylsilyl)methyl group of the Bbt group. On heating, the hydridoplatinum complex 2 underwent further intramolecular Si-C activation giving another type of platinacycle, [PtMe{SiMe2CH(SiMe3)C6H2-3CH(SiMe3)2-5-C(SiMe3)3-2-P(Me)CH2CH2(Me)PBbt}] (4), which has a (methyl)(silyl)¬platinum complex structure.