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Reaction of the sodium bis(iminophosphoranyl)alkanide compounds Na[CR‘‘(PPh2NC6H4R‘-4)2] (1a, R‘‘ = H, R‘ = CH3; 1b, R‘‘ = H, R‘ = OCH3; 1c, R‘‘ = CH3, R‘ = CH3) with M2X4(PR3)2 (M = Pt, Pd; X = Cl, Br; PR3 = PEt3, PMe2Ph) yields the four-membered metallacycles MX(PR3){CR‘‘(PPh2NC6H4R‘-4)2} (2a−f, M = Pt; 3a−c, M = Pd), containing the bis(iminophosphoranyl)alkanide ligand coordinated in a σ-C,σ-N chelating fashion. The molecular structure of 2e (X = Cl, PR3 = PMe2Ph, R‘‘ = CH3, R‘ = CH3) has been determined by X-ray crystallography. The 1,1-bis(iminophosphoranyl)ethanide ligand (1c) in 2e is σ-C,σ-N-chelated toward the square-planar-surrounded Pt, with N coordinated trans to PMe2Ph (Pt−N = 2.132(4) A) and C trans to Cl (Pt−C = 2.116(4) A), resulting in a puckered M−N−P−C metallacycle and one noncoordinated phosphinimine moiety. In solution the complexes 2 and 3 undergo a dynamic process, involving an intermediate (for 2) or fast (for 3) N,N‘ exchange of coordinated and noncoordinated PN groups. Heating (t...

organometallics

Reactions of Sodium Bis(<i>N</i>-aryliminophosphoranyl)alkanides with Halide-Bridged Platinum(II) and Palladium(II) Phosphine Dimers Affording Four-Membered M−N−P−C Metallacycles and Orthometalated Platinum(II) and Palladium(II) Complexes

Reactions of Sodium Bis(N-aryliminophosphoranyl)alkanides with Halide-Bridged Platinum(II) and Palladium(II) Phosphine Dimers Affording Four-Membered M−N−P−C Metallacycles and Orthometalated Platinum(II) and Palladium(II) Complexes