Ni, Pd and Pt pincer complexes of 2-(diphenylphosphanyl)--(2-(diphenyl-phosphanyl)benzyl)benzamide: synthesis, reactivity and catalytic studies.

In this article, the synthesis of bis(phosphine), -PhPCHC(O)N(H)CHCHPPh- (1) (hereafter referred to as "PNHP" and its anionic form as "PNP") and its group 10 metal chemistry and catalytic studies are described. PNHP (1) on reaction with NiCl(DME) and PdCl(COD) afforded pincer complexes, [MCl{(PNP)κ-,,}] (M = Ni, 2; Pd, 3). A similar reaction of 1 with PtCl(COD) yielded a chelate complex, [PtCl{(PNHP)κ-,}] (4), which on further treatment with LiHMDS produced the 1,2-azaphospholene-phosphine complex, [PtCl(Ph){(-P(Ph)CHCONCHCHPPh-)κ-,}] (5) P-C/P-N bond metathesis.

Cu-Amidobis(phosphine)-Catalyzed Direct Amidation of Unactivated Alkanes via C(sp)-H Activation.

Herein, we describe an acid-base-free, sustainable, and efficient method for direct amidation of unactivated alkanes and toluene derivatives, using the dimeric Cu complex [Cu{-PhPCHCONCHPPh-}] (here onward referred to as [PNP-Cu]). Using this method, C(sp)-N bond formation was achieved through the activation of very challenging C(sp)-H bonds in cycloalkanes, alkenes, allyl groups, and benzyl groups, with tolerance toward ketonic groups, heterocycles, and halide functionalities. One of the precatalysts, (PNHP-Cu-Npht) was isolated and structurally characterized.