Synthesis of a Heterometallic Trinuclear Cluster of Ruthenium and Platinum with a Linear Alignment

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• 作者：Takuya Kuzutani ; Yushi Torihata ; Hiroharu Suzuki ; Toshiro Takao
• 刊名：Organometallics
• 出版年：2016
• 出版时间：August 8, 2016
• 年：2016
• 卷：35
• 期：15
• 页码：2543-2556
• 全文大小：724K
• 年卷期：0
• ISSN：1520-6041

文摘

A heterobimetallic trinuclear complex of Ru and Pt in a linear alignment, {Cp*Ru(H)₂}₂(Pt)(μ-P^tBu₂)₂(μ-H)₂ (2; Cp* = η⁵-C₅Me₅), was synthesized via P–C bond scission upon the photolysis of Cp*Ru(μ-H)₄RuCp* (1) in the presence of Pt(P^tBu₃)₂. Complex 2 was alternatively synthesized by the reaction of 1 with Pt(P^tBu₂H)₃, together with the formation of a triangular Ru₂Pt complex, (Cp*Ru)₂{Pt(P^tBu₂H)}(μ-P^tBu₂)(μ-H)₃(H)₂ (4). X-ray diffraction experiments showed that the structure of 2 could be regarded as a dimer of [Cp*RuH₃(P^tBu₂)]⁻ fragments linked by a Pt²⁺ ion. In contrast to the relevant monometallic trihydrido complex of ruthenium, Cp*RuH₃(P^tR₃), terminal hydrides of 2 were readily substituted by CO and ethylene, leading to the formation of {Cp*Ru(L)}₂(Pt)(μ-P^tBu₂)₂(μ-H)₂ (5; L = CO, 6; L = C₂H₄). Such high reactivity could be attributed to the facile formation of a coordinatively unsaturated intermediate owing to stabilization by bulky μ-P^tBu₂ moieties as well as electronic influence of the central Pt atom. In fact, terminal hydrides of 2 were readily removed upon evacuation, leading to the formation of tetra- and dihydrido complexes (Cp*Ru){Cp*Ru(H)₂}Pt(μ-P^tBu₂)₂(μ-H)₂ (3) and (Cp*Ru)₂Pt(μ-P^tBu₂)₂(μ-H)₂ (8), consecutively. Upon hydrogenation, 3 and 8 were smoothly transformed into 2. In contrast with the reactions of 2 with 2e donors, substitution at the Pt atom occurred in reactions with Ph₂SiH₂ and Et₂SiH₂, resulting in μ-silylene and μ-silyl complexes {Cp*Ru(H)}{Cp*Ru(P^tBu₂H)}Pt(μ-P^tBu₂)(μ-SiPh₂)(μ-H)₂ (9) and {Cp*Ru(H)₂}{Cp*Ru(P^tBu₂H)}Pt(μ-P^tBu₂)(μ-η²-SiEt₂)(μ-H)₂ (10), respectively. In these reactions, the μ-phosphido ligand bridging the Ru and Pt atoms was transformed into a terminal phosphine ligand at the peripheral Ru atom, alongside the formation of μ-silylene and μ-silyl ligands via reductive P–H bond formation.