Issue 9, 2003

New phosphino-oxazoline and related phosphino-iminolate palladium complexes; structure of an unusual zwitterionic dinuclear Pd(ii) complex

Abstract

Reaction of the phosphino-oxazoline chiral ligand (4-(R)-phenyl-2-oxazoline-2-ylmethyl)diphenylphosphine) (abbreviated (R)-PCH2oxPh) with [Pd(dmba-C,N)(μ-Cl)]2 or [PdCl2(cod)] (cod = 1,5-cyclooctadiene) led to the formation of [Pd(dmba-C,N){(R)-PCH2oxPh2P,N}]Cl 1 and [PdCl2{(R)-PCH2oxPh2P,N}] 5, respectively. Deprotonation of the palladium phosphino-oxazoline complex 1 occurred at the PCH2 group and resulted in the formation of an anionic P,N chelate with a prochiral carbon atom in [Pd(dmba-C,N){(R)-PCHoxPh2P,N}] 2. Reaction of 2 with [Pd(dmba-C,N)(μ-Cl)]2 led to the unexpected and diastereoselective formation of the dinuclear complex [{[upper bond 1 start]Pd(dmba-C,N)Cl}-(R)-{C[upper bond 1 end]H[upper bond 1 start]PPh2-(R)-oxPh}Pd[upper bond 1 end](dmba-C,N)] 4 in which a Pd(dmba-C,N)Cl moiety is directly bonded to the carbon α to the P atom of the anionic P,N chelate of 2. This results in an unsual zwitterionic structure. In the course of this work, crystals of [(dmba-C,N)Pd(μ-OH)(μ-Cl)Pd(dmba-C,N)]·1/2[Pd(dmba-C,N)(μ-Cl)]27 were obtained and the single crystal X-ray analyses of complexes 2, 4·2THF, 5·CH2Cl2, [PdCl(Me){(R)-PCH2oxPh2P,N}] 6 and 7 are presented.

Graphical abstract: New phosphino-oxazoline and related phosphino-iminolate palladium complexes; structure of an unusual zwitterionic dinuclear Pd(ii) complex

Supplementary files

Article information

Article type
Paper
Submitted
09 Jan 2003
Accepted
14 Mar 2003
First published
03 Apr 2003

Dalton Trans., 2003, 1669-1674

New phosphino-oxazoline and related phosphino-iminolate palladium complexes; structure of an unusual zwitterionic dinuclear Pd(II) complex

A. Apfelbacher, P. Braunstein, L. Brissieux and R. Welter, Dalton Trans., 2003, 1669 DOI: 10.1039/B300321N

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