title: Silyl, hydrido-silylene, or other bonding modes: some unusual structures of [(dhpe)Pt(SiHR2)]+ (dhpe = H2P-CH2-CH2-PH2; R = H, Me, SiH3, Cl, OMe, NMe2) and [(dhpe)Pt(SiR3)](+) (R = Me, Cl) from DFT calculations.
abstract: DFT (B3LYP) calculations have been carried out in order to quantitatively evaluate the energies and stereochemistry of the accessible structures of [(dhpe)Pt(SiHR(2))](+) (dhpe = H(2)P-CH(2)-CH(2)-PH(2); R = H, CH(3), SiH(3), Cl, OMe, SMe, NMe(2)) and of [(dhpe)Pt(SiR(3))](+) (R = CH(3), Cl). A number of different isomers have been located. The expected terminal silyl or hydrido-silylene complexes are often not the most stable complexes. An isomer in which an H or an R group bridges a Pt=SiHR or Pt=SiR(2) bond is found to compete with the terminal silyl or hydrido-silylene isomers. In some cases, isomers derived from cleavage of a C-H bond and formation of a silene or disilene ligand are obtained. The structures of the platinum silyls differ from that of the equivalent alkyl complex, calculated for [(dhpe)Pt(CH(3))](+).
authors.affiliation: Unitat de Química Física, Edifici C.n., Universitat Autònoma de Barcelona, 08193 Bellaterra, Catalonia, Spain.
authors.forename: Maria
authors.initials: M
authors.lastname: Besora
authors.forename: Feliu
authors.initials: F
authors.lastname: Maseras
authors.forename: Agustí
authors.initials: A
authors.lastname: Lledós
authors.forename: Odile
authors.initials: O
authors.lastname: Eisenstein