PREPARATION AND CHARACTERIZATION OF ((PRO)-PR-I)(4)WW(ETA(2)-DMPE)(2)(CO), (ETA(1)-O2CH)((PRO)-PR-I)(4)WW(ETA(2)-DMPE)(2)(H), [H(ETA(2)-DMPE)WWO2](2)(MU-O), AND W-2(O)(4)(MU-O)[W(ETA(2)-DMPE)(2)CO](2) (DMPE = BISDIMETHYLPHOSPHINOMETHANE), COMPOUNDS WITH W-W BONDS BETWEEN METAL ATOMS IN GREATLY DIFFERING OXIDATION-STATES

The compound W-2(H)(2)((OPr)-Pr-i)(4)(eta(2)-dmpe)(2) reacts in hydroc arbon solutions with CO, CO2, and H2O to give ((PrO)-Pr-i)(4)WW(eta(2) -dmpe)(2)(CO), 1, (eta(1)-O2CH)((PrO)-Pr-i)(4)WW(eta(2)-dmpe)(2)H, 2, and [H(eta(2)-dmpe)(2)WWO2](2)(mu-O), 3, respectively. Compound 1 reac ts with H2O in hydrocarbon solvents to give W-2(O)(4)(mu-O) [W(eta(2)- dmpe)(2)(CO)](2), 4. The compounds 1-4 contain unsupported W-W bonds b etween metal atoms in greatly different oxidation states. The new comp ounds have been characterized by NMR and infrared spectroscopy, and co mpounds 1 and 4, by single-crystal X-ray studies. For 1.0.5toluene at -171 degrees C, a = 19.546(3) Angstrom, b = 21.745(4) Angstrom, c = 18 .114(3) Angstrom, Z = 8, and space group Pcab and for 4.4CH(2)Cl(2) at -169 degrees C, a = 13.282(2) Angstrom, b = 14.308(3) Angstrom, c = 1 5.319(3) Angstrom, beta = 97.88(1)degrees, Z = 2, and space group P2(1 )/n.