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• W2034390565 abstract "The reactions of the sterically demanding group-13 alkyls ER3 (E = Al, Ga, In; R = CH2 t-Bu, CH2SiMe3) with the platinum-complex [(dcpe)Pt(H)(CH2t-Bu)] were re-investigated. The bimetallic compounds [(dcpe)Pt(ER2)(R)] (3: E = Ga, R = CH2SiMe3; 5: E = In, R = CH2t-Bu; dcpe = bis(dicyclohexylphosphino)ethane) with direct σ(Pt–E) bonds were obtained by oxidative addition of an E-C bond to the coordinatively unsaturated fragment [(dcpe)Pt] produced in situ by thermolysis of the starting complex [(dcpe)Pt(CH2t-Bu)(H)]. The single crystal structure determination reveals a Pt–Ga bond length of 2.376(2) Å and a Pt–In bond length of 2.608(1) Å. All new compounds were characterised by elemental analysis, 31P and 195Pt NMR spectroscopy. Interestingly, the Pt–Ga compound 3 slowly transforms into the platinum alkyl/hydride isomer {(dcpe)Pt(μ2-H)[CH2Si(CH3)2 CH2Ga(CH2SiMe3)2]} (4) during crystallization from solution at room temperature. The X-ray single crystal structure analysis revealed both complexes 3 and 4 coexisting in the unit cell in a 1:1 relation. The inaccessibility of analytically pure samples of the Pt–Al complex {(dcpe)Pt[Al(CH2t-Bu)2](CH2t-Bu)} (6), postulated as intermediate of the reaction of [(dcpe)Pt(H)(CH2t-Bu)] with Al(CH2t-Bu) on the basis of 31P and 195Pt NMR data, is attributed to an enhanced tendency to isomerisation into the alkyl/hydride Pt/Al congener of 4. A brief DFT analysis of the bonding situation of the model complex [(dhpe)Pt(GaMe2)(Me)] (1M) revealed, that the contribution of π(Pt–Ga) back-bonding is negligible." @default.
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• W2034390565 date "2004-11-01" @default.
• W2034390565 modified "2023-10-18" @default.
• W2034390565 title "The reaction of the group-13 alkyls ER3 (E=Al, Ga, In; R=CH2t-Bu, CH2 SiMe3) with the platinum-complex [(dcpe)Pt(H)(CH2t-Bu)]" @default.
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• W2034390565 doi "https://doi.org/10.1016/j.jorganchem.2004.09.059" @default.
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