FORMATION OF COORDINATEDt-Bu2P(H)OviaREACTION OFt-Bu2PCI WITH ETHANOLIC ReO4−. SYNTHESIS AND STRUCTURE OFtrans-ReOCl2(OEt){t-Bu2P(OEt)}{t-Bu2P(H)O}

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Abstract
Reaction of t-Bu2PCl with KReO4 (3:1) in ethanol at room temperature results in the formation of trans-ReOCl2(OEt){t/-Bu2P(OEt)} {t-Bu2P(H)O} in 65% yield. The structure of this purple, hexane-soluble crystalline material has been determined by X-ray crystallography. The compound crystallizes in the space group P21/n with a = 12.762 (5), b = 15.919 (4), c = 15.103(2) Å, β = 109.34(5)°, and Z = 4. The structure was refined to R = 0.066 (R w = 0.071) for 1968 independent reflections. The molecular structure consists of a rhenium atom in a distorted octahedral geometry. Two Cl atoms are trans to each other as are the Re = O and Re-O-Et units. The Re = O and Re-O-Et lengths (1.69(2) and 1.85(2) Å) and the geometry about the ethoxide oxygen atom indicate a considerable degree of M–O multiple bonding for both of these units. Thet-Bu2P(H)O and t-Bu2,P(OEt) units are mutually trans and behave as neutral, two-electron donors to the Re(V) center.