Reactions of palladium germylene complexes: formation of sulfide bridges

Zuzanna T Cygan; Jeff W Kampf; Mark M Banaszak Holl

doi:10.1021/ic034613z

Reactions of palladium germylene complexes: formation of sulfide bridges

Inorg Chem. 2003 Nov 3;42(22):7219-26. doi: 10.1021/ic034613z.

Authors

Zuzanna T Cygan¹, Jeff W Kampf, Mark M Banaszak Holl

Affiliation

¹ Department of Chemistry, University of Michigan, Ann Arbor, Michigan 48109-1055, USA.

PMID: 14577791
DOI: 10.1021/ic034613z

Abstract

Reactivity of three novel Pd germylene species is presented. (Et(3)P)(2)PdGe[N(SiMe(3))(2)](2) (1) and (dppe)PdGe[N(SiMe(3))(2)](2) (6) react with COS to give the sulfide bridged species (Et3P)2Pd(mu S)Ge[N(SiMe3)2]2 (2) and (dppe)Pd(mu S)Ge-[N(SiMe3)2]2 (7) (dppe = (diphenylphosphino)ethane). (Ph(3)P)(2)PdGe[N(SiMe(3))(2)](2) (4) reacts with COS to give the disulfide bridged complex (Ph(3)P)(2)Pd(muS)(2)Ge[N(SiMe(3))(2)](2) (5) resulting in Pd-Ge bond cleavage. This phosphine dependent reactivity is explored. Crystal structures of 2, 5, 7, and the dimeric form of complex 2, (8), are reported. In the presence of excess germylene, complexes 2 and 5 are shown to partially regenerate their parent palladium germylene complexes, 1 and 4, respectively, via photolysis or heating.