Abstract
A review of all of the known structural stereotypes of dimeric Pt(I) or Pd(I) systems with at least one bridging phosphido group is presented. The nature of the direct metal-metal interaction is affected by the number, nature, and disposition of the various coligands. It appears that in some cases a bent M-M bond is by itself a center of nucleophilicity. On the other hand, it is experimentally known that the bridging phosphido ligand is a competing nucleophile, giving rise to an agostic interaction in Pd(2), but not in Pt(2), derivatives. MO theory is used to outline the major electronic features and correlation between different prototypes. Besides a qualitative approach based on the EHMO method, DFT and MP2 methods were used to reproduce the experimental structures and to explore the possibility of unknown tautomers.
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