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The reaction of [Ru(PPh 3 ) 3 Cl 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 PhC[triple bond, length as m-dash]CH added across the Ru-Zn bond of 1, and also reversed the phosphine cyclometallation, to give [Ru(dppbz)(Ph 2 P(biphenyl))(H) 2 (H)(ZnMe)] (4) and [Ru(dppbz)(Ph 2 P(biphenyl))(C[triple bond, length as m-dash]CPh) 2 (H)(ZnMe)] (5) respectively.

Transforming PPh3into bidentate phosphine ligands at Ru–Zn heterobimetallic complexes

Transforming PPh₃into bidentate phosphine ligands at Ru–Zn heterobimetallic complexes