title: Planar PtPd3Complexes Stabilized by Three Bridging Silylene Ligands.
abstract: A heterobimetallic PtPd3complex supported by three bridging diphenylsilylene ligands, [Pt{Pd(dmpe)}3(μ3-SiPh2)3] (1, dmpe=1,2-bis(dimethylphosphino)ethane), has been synthesized from mononuclear Pd and Pt complexes. The hexagonal core composed of Pt, Pd, and Si atoms is slightly larger than that of the tetrapalladium complex, [Pd{Pd(dmpe)}3(μ3-SiPh2)3] (2). Reaction of PhSiH3with complex 1 in the presence and absence of Ph2SiH2results in the formation of a tetranuclear complex with silyl and hydride ligands at the Pt center, [PtH(SiPh2H){Pd(dmpe)}3(μ3-SiHPh)3] (3), and an octanuclear complex, [{Pt{Pd(dmpe)}3(μ3-SiHPh)3}2(κ2-dmpe)] (5), respectively. Both M-Si (M=Pt, Pd) bond lengths and the29Si NMR chemical shifts of 1 and 2 are located between those of mononuclear late transition-metal complexes with a silylene ligand and complexes with donor-stabilized silylene ligands. CuI and AgI adducts of 1 and 2, formulated as [M(μ-M'I){Pd(dmpe)}3(μ3-SiPh2)3] (M=Pt, Pd; M'=Cu, Ag), undergo elimination of CuI (AgI) and regenerate the tetrametallic complexes upon heating or addition of a chelating diphosphine. Elimination of AgI from 2-AgI occurs more rapidly than elimination of CuI from 2-CuI, as determined from the results of kinetics experiments.
authors.affiliation: Laboratory for Chemistry and Life Science, Institute of Innovative Research, Tokyo Institute of Technology, 4259-R1-3 Nagatsuta, Midori-ku, Yokohama, 226-8503, Japan.
authors.forename: Makoto
authors.identifier: http://orcid.org/0000-0001-8248-0535
authors.initials: M
authors.lastname: Tanabe
authors.affiliation: Laboratory for Chemistry and Life Science, Institute of Innovative Research, Tokyo Institute of Technology, 4259-R1-3 Nagatsuta, Midori-ku, Yokohama, 226-8503, Japan.
authors.forename: Ryouhei
authors.initials: R
authors.lastname: Yumoto
authors.affiliation: Laboratory for Chemistry and Life Science, Institute of Innovative Research, Tokyo Institute of Technology, 4259-R1-3 Nagatsuta, Midori-ku, Yokohama, 226-8503, Japan.
authors.forename: Tetsuyuki
authors.initials: T
authors.lastname: Yamada
authors.affiliation: Laboratory for Chemistry and Life Science, Institute of Innovative Research, Tokyo Institute of Technology, 4259-R1-3 Nagatsuta, Midori-ku, Yokohama, 226-8503, Japan.
authors.forename: Tomoko
authors.initials: T
authors.lastname: Fukuta
authors.affiliation: Laboratory for Chemistry and Life Science, Institute of Innovative Research, Tokyo Institute of Technology, 4259-R1-3 Nagatsuta, Midori-ku, Yokohama, 226-8503, Japan.
authors.forename: Tsuyoshi
authors.initials: T
authors.lastname: Hoshino
authors.affiliation: Laboratory for Chemistry and Life Science, Institute of Innovative Research, Tokyo Institute of Technology, 4259-R1-3 Nagatsuta, Midori-ku, Yokohama, 226-8503, Japan.
authors.forename: Kohtaro
authors.identifier: http://orcid.org/0000-0003-0538-9978
authors.initials: K
authors.lastname: Osakada
authors.affiliation: Department of Chemistry, Faculty of Science, Nara Woman's University, Kitauoya-higashi-machi, Nara, 630-8506, Japan.
authors.forename: Tomoaki
authors.initials: T
authors.lastname: Tanase
keywords: NMR spectroscopy; multinuclear complexes; palladium; platinum; silylene ligands