SELECTIVE C-CL VERSUS P-CL ACTIVATION-SYNTHESES OF COMPLEXES WITH P-CL FUNCTIONAL PHOSPHINOMETHYL BRIDGES ETA(2),MU(2)-(P(R)CL-CH2)

On reaction of chloromethylchlorophosphines Cl(R)P-CH2-Cl with Pd(Ph3P )(4) the C-Cl bond is selectively activated by oxidative addition to P d(0), unusual dipalladium complexes with P-Cl functional eta(2),mu(2){ CH2-P(R)Cl} bridges being formed with high diastereoselectivity. The X -ray structure of 3a (R = tBu) reveals a chair-shaped Pd2P2C2 six-memb ered ring system with the substituents (Cl, tBu) at the two m(2)-P ato ms in cis-position. (C) 1998 Elsevier Science S.A. All rights reserved .