The reactions of Re2X4(�-diphosphine)2 with (C6H5)2CHCN (where X= Cl or Br and diphosphine = bis-(diphenylphosphino)methane or 1,1-bis-(diphenylphosphino)ethane) have been explored. Dirhenium complexes [Re2X3(�-diphosphine)2((C6H5)2CHCN)2]PF6, have been prepared which exhibit asymmetry between the two Rhenium atoms. One of the Rhenium atoms in the Re24+ core has a coordination number of five; the other rhenium atom has a coordination number of six. The five-coordinate rhenium is bonded to the other rhenium, two halides, and two phosphorus atoms from the bridging diphosphine. The six-coordinate rhenium is bonded to one rhenium, one halide, two phosphorus, and two nitrogen atoms. The nitrogen atoms are from the two diphenylacetonitrile ligands. Infrared Spectroscopy, Proton NMR, Phosphorus-31 NMR, Carbon-13 NMR, Ultraviolet-visible spectroscopy, Cyclic Voltametry, and electro spray Mass Spectrometry are all in accord with the proposed structure.  Compounds of this type have been previously shown to interact with small organic molecules. The relatively sterically demanding diphenylacetonitrile ligand may make a good leaving group in further synthetic work.

Reactions of dirhenium phosphine complexes with diphenylacetonitrile

245th National Meeting (2013)

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