Net heterolytic cleavage of B-H and B-B bonds across the N-Pd bond in a cationic (PNP)Pd fragment. Academic Article uri icon

abstract

  • The use of weakly coordinating anions BAr(F)(4) (where Ar(F) = 3,5-(CF(3))(2)C(6)H(3)) and CB(11)H(12) allows one to access clean reactions of the [(PNP)Pd](+) fragment (PNP = bis(2-(i)Pr(2)P4-Me-phenyl)amido) with the B-H bond in catecholborane (CatBH) and catecholdiboron (CatBBCat). In both cases, a net heterolytic cleavage of B-H or B-B takes place, with the nitrogen atom of PNP being a recipient of a boryl fragment. The resultant products [(PN(BCat)P)PdH](+) (2) and [(PN(BCat)P)PdBCat](+) (3) were isolated as either BAr(F)(4) or CB(11)H(12) salts and fully characterized. They are susceptible to hydrolysis, with the B-N bond hydrolyzing selectively and rapidly at RT to give [(PN(H)P)PdH](+) (1) and [(PN(H)P)PdBCat](+) (4). Notably, 4 and 2 are isomers, but they do not interconvert even under thermolysis at 90 C. The Pd-B bond in 4 can be further hydrolyzed more slowly, to give 1. On the other hand, a Pd-B bond was formed from the Pd-H bond in 2 by reaction with excess CatBH (and evolution of H(2)), producing 3.

published proceedings

  • Inorg Chem

author list (cited authors)

  • Zhu, Y., Chen, C., Fafard, C. M., Foxman, B. M., & Ozerov, O. V.

citation count

  • 29

complete list of authors

  • Zhu, Yanjun||Chen, Chun-Hsing||Fafard, Claudia M||Foxman, Bruce M||Ozerov, Oleg V

publication date

  • August 2011