摘要:
The new bis(phosphino) amido ligand, [MePNPPh], that incorporates (i) an ortho-tolylene linker between nitrogen and phosphorus and (ii) phenyl substituents on phosphorus, has been synthesized as its protonated derivative, [MePNPPh] H, via sequential treatment of (2-Br, 4-Me-C6H3)(2)NH with (i) (BuLi)-Li-n, (ii) Ph2PCl and (iii) HCl. Deprotonation of [MePNPPh]H with (BuLi)-Li-n in THF affords the lithium derivative which has been isolated as both mono and bis THF adducts, [MePNPPh]Li(THF) and [MePNPPh]Li(THF)(2). Treatment of [MePNPPh]Li(THF)(2) with GaCl3 and InX3 (X = Cl, Br, I) gives a series of [MePNPPh]MX2 complexes in which the [PNP] donor binds in a "T"-shaped manner and the metal has a distorted trigonal bipyramidal geometry. The reaction of [MePNPPh]Li(THF)(2) with "GaI" yields the Ga-Ga bonded complex [kappa(2)-MePNPPh](GaI)(GaI)[kappa(2)-MePNPPh] in which the [MePNPPh] ligand binds in a kappa(2)-P,N manner. The bis(phosphino) amine [MePNPPh]H may also serve as a ligand and treatment of [MePNPPh]H with GaBr3 affords [kappa(2)-{[MePNPPh]H}GaBr2][GaBr4], in which the [MePNPPh]H ligand coordinates in a kappa(2)-P,P manner such that the gallium adopts a tetrahedral geometry. (C) 2010 Elsevier B.V. All rights reserved.