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Cationic Platinum(II) σ‐SiH Complexes in Carbon Dioxide Hydrosilation
Author(s) -
Ríos Pablo,
Díez Josefina,
LópezSerrano Joaquín,
Rodríguez Amor,
Conejero Salvador
Publication year - 2016
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201603524
Subject(s) - agostic interaction , cationic polymerization , chemistry , platinum , silanes , hydrosilylation , hydride , silylation , bar (unit) , medicinal chemistry , crystallography , polymer chemistry , catalysis , silane , organic chemistry , metal , physics , meteorology
The low‐electron‐count cationic platinum complex [Pt(I t Bu’)(I t Bu)][BAr F ], 1 , interacts with primary and secondary silanes to form the corresponding σ‐SiH complexes. According to DFT calculations, the most stable coordination mode is the uncommon η 1 ‐SiH. The reaction of 1 with Et 2 SiH 2 leads to the X‐ray structurally characterized 14‐electron Pt II species [Pt(SiEt 2 H)(I t Bu) 2 ][BAr F ], 2 , which is stabilized by an agostic interaction. Complexes 1 , 2 , and the hydride [Pt(H)(I t Bu) 2 ][BAr F ], 3 , catalyze the hydrosilation of CO 2 , leading to the exclusive formation of the corresponding silyl formates at room temperature.