The first examples of amido phosphine complexes of zinc have been prepared. Addition of N-(2-diphenylphosphinophenyl)-2,6-diisopropylaniline (H[NP]) to ZnMe(2) or ZnEt(2) in diethyl ether at -35 degrees C generated the monomeric, three-coordinate [NP]ZnR (R = Me, Et), while the metathesis reaction of ZnCl(2) with [NP]Li(THF)(2) in diethyl ether at -35 degrees C produced homoleptic [NP](2)Zn.

The amido diphosphine complexes [PNP]PtMe and [PNP]PtOTf, where [PNP]- is bis(2-diphenylphosphinophenyl)amide, effectively activate the benzene C-H bond in the presence of an appropriate Lewis acid or base, leading to the formation of [PNP]PtPh quantitatively.

A series of diamagnetic divalent nickel complexes supported by bidentate diarylamido phosphine ligands have been prepared and characterized. Deprotonation of N-(2-diphenylphosphinophenyl)-2,6-diisopropylaniline (H[ i Pr-NP]) and N-(2-diphenylphosphinophenyl)-2,6-dimethylaniline (H[Me-NP]) with n-BuLi in THF at -35 °C produced the corresponding lithium complexes, [ i Pr-NP]Li(THF) 2 and [Me-NP]Li(THF) 2 , respectively. The chloride complex {[ i Pr-NP]NiCl} 2 is accessible from the reaction of NiCl 2 (DME) with [ i Pr-NP]Li(THF) 2 or H[ i Pr-NP] in the presence of triethylamine. Addition of PMe 3 to {[ i Pr-NP]NiCl} 2 afforded [ i Pr-NP]NiCl(PMe 3 ), from which [ i Pr-NP]NiMe(PMe 3 ), [ i Pr-NP]NiPh(PMe 3 ), and [ i Pr-NP]-Ni(η 3 -CH 2 Ph) were prepared from the metathetical reactions with appropriate Grignard reagents. Solution NMR data of [ i Pr-NP]NiMe(PMe 3 ) revealed two geometric isomers at room temperature with the major species carrying PMe 3 cis to the phosphorus donor of the amido phosphine ligand. Interestingly, only one of the possible isomers is observed for [ i Pr-NP]-NiCl(PMe 3 ) and [ i Pr-NP]NiPh(PMe 3 ), in which the two phosphorus donors in the former are exclusively cis whereas those in the latter are trans. The benzyl complexes [ i Pr-NP]Ni(η 3 -CH 2 Ph) and [Me-NP]Ni(η 3 -CH 2 Ph) are prepared directly from the reactions of [ i Pr-NP]Li-(THF) 2 and [Me-NP]Li(THF) 2 , respectively, with Ni(COD) 2 in the presence of benzyl chloride. The η 3 -feature of the benzyl ligand maintained in solution is elucidated by the 1 J CH value observed for the benzylic methylene group in the NMR spectroscopy. In addition to the spectroscopic data for all new molecules, X-ray structures of H[ i Pr-NP], [Me-NP]Li(THF) 2 , [ i Pr-NP]NiCl(PMe 3 ), [ i Pr-NP]NiMe(PMe 3 ), [ i Pr-NP]NiPh(PMe 3 ), [ i Pr-NP]Ni(η 3 -CH 2 Ph), and [Me-NP]Ni(η 3 -CH 2 Ph) are presented.

The palladium-catalyzed aryl amination of 1-bromo-2-fluorobenzene with N,N-dimethylethylenediamine quantitatively produces N-(dimethylaminoethyl)-2-fluoroaniline, which subsequently reacts with KPPh2 in 1,4-dioxane to afford N-(dimethylaminoethyl)-2-diphenylphosphinoaniline (H[PNN]). The reactions of trialkylaluminium with H[PNN] in toluene generate the corresponding aluminium dialkyl complexes [PNN]AlR2 (R = Me, Et, i-Bu). The solution NMR spectroscopic and X-ray crystallographic studies are indicative of a trigonal bipyramidal geometry for these aluminium complexes in which the amino nitrogen atom is trans to the phosphorus donor of the [PNN]- ligand. This study presents rare examples of structurally characterized, five-coordinate aluminium hydrocarbyl complexes supported by phosphine-derived ligands.