Transforming PPh3 into Bidentate Phosphine Ligands at Ru-Zn Heterobimetallic Complexes

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Abstract

The reaction of [Ru(PPh 3) 3Cl 2] with excess ZnMe 2 led to P-C/C-H bond activation and P-C/C-C bond formation to generate a chelating diphenylphosphinobenzene ligand as well as a cyclometallated (diphenylphosphino)biphenyl group in the final product of the reaction, [Ru(dppbz)(PPh 2(biphenyl)′)(ZnMe)] (1; dppbz = 1,2-bis(diphenylphosphino)benzene); PPh 2(biphenyl)′ = cyclometallated PPh 2(biphenyl). The mechanism of reaction was studied and C-C coupling to give a bidentate 2,2′-bis(diphenylphosphino)biphenyl (BIPHEP) ligand was suggested to be one of the key steps of the process. This was confirmed by the reaction of [Ru(BIPHEP)(PPh 3)HCl] with ZnMe 2, which also gave 1. An analogous set of steps took place upon addition of ZnMe 2 to [Ru(rac-BINAP)(PPh 3)HCl] (rac-BINAP = racemic(2,2′-bis(diphenylphosphino)-1,1′-binaphthyl) to give [Ru(dppbz)(PPh 2(binaphthyl)′)ZnMe] (3). H 2 and the C-H bond of PhCCH added across the Ru-Zn bond of 1, and also reversed the phosphine cyclometallation, to give [Ru(dppbz)(Ph 2P(biphenyl))(H) 2(H)(ZnMe)] (4) and [Ru(dppbz)(Ph 2P(biphenyl))(CCPh) 2(H)(ZnMe)] (5) respectively.

Original languageEnglish
Pages (from-to)14000-14009
Number of pages10
JournalDalton Transactions
Volume48
Issue number37
Early online date26 Aug 2019
DOIs
Publication statusPublished - 24 Sep 2019

ASJC Scopus subject areas

  • Inorganic Chemistry

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