ChemInform Abstract: IR Spectroelectrochemistry of η3-Allyl Dicarbonyl Complexes of Molybdenum(II) and Tungsten(II).

ChemInform Abstract

The electrooxidation of the title complexes (I) is studied by FTIR spectroscopy coupled with an optically transparent thin-layer (OTTLE) cell. The N-ligand complexes for M: Mo undergo a one-electron oxidation to form paramagnetic monocations, which are generally stable in solution. Some of them are isolated as their PF₆ salts with ca. 80% yield. The P- or As-ligand complexes undergo one-electronoxidations to give unstable monocations. In the case of M: Mo and L: Ph₂P-(CH2)n-PPh2 (n = 1, 2) the monocations decompose rapidly to give the ions (η3-allyl-Mo(CO)3L)+ as the predominant final product together with Mo(IV) and/or Mo(V) carbonyl-containing species. The cations of (Ic) and (If) also decompose leading to seven-coordinate η1-allyl-MCl(CO)3L complexes as the major product.