Effect of bulky alkyl substituents on the dynamics and stability of platinum complexes with β-agostic bonding

Abstract
Protonation of the platinum(0) compounds [Pt(CH2 CHBut)(P–P)][P–P = But 2P(CH2)nPBut 2, n= 2 1a or 3 1b, or But 2PCH2C6H4CH2PBut 21c] with HBF4·OMe2 in diethyl ether at 273 K afforded the pale yellow cationic complexes [PtH(CH2 CHBut){But 2P(CH2)2PBut 2}][BF4]2a and [Pt(C6H13)(P–P)][BF4][P–P = But 2P(CH2)3PBut 22b or But 2PCH2C6H4CH2PBut 22c] respectively. Complex 2a has been shown by IR and NMR studies to possess a cis alkene–hydride ground-state structure, whilst 2b and 2c achieve a 16-electron configuration via a β-C–H agostic interaction. The reaction between the red dinuclear complex [Pt2(µ-H)2(dbpp)2][BF4]2[dbpp = But 2P(CH2)3PBut 2] and 2,3,3-trimethylbut-1-ene afforded the complex [Pt(CH2CHMeBut)(dbpp)][BF4]2d which also exhibits a β-C–H agostic interaction.

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