Preparation and Characterization of ( i PrO) 4 WW(η 2 -dmpe) 2 (CO), (η 1 -O 2 CH)( i PrO) 4 WW(η 2 -dmpe) 2 (H), [H(η 2 -dmpe)WWO 2 ] 2 (μ-O), and W 2 (O) 4 (μ-O)[W(η 2 -dmpe) 2 CO] 2 (dmpe = Bisdimethylphosphinomethane), Compounds with W−W Bonds between Metal Atoms in Greatly Differing Oxidation States
1998; American Chemical Society; Volume: 37; Issue: 7 Linguagem: Inglês
10.1021/ic9705249
ISSN1520-510X
AutoresMalcolm H. Chisholm, Kirsten Folting, Keith S. Kramer, William E. Streib,
Tópico(s)Metalloenzymes and iron-sulfur proteins
ResumoThe compound W2(H)2(OiPr)4(η2-dmpe)2 reacts in hydrocarbon solutions with CO, CO2, and H2O to give (iPrO)4WW(η2-dmpe)2(CO), 1, (η1-O2CH)(iPrO)4WW(η2-dmpe)2H, 2, and [H(η2-dmpe)2WWO2]2(μ-O), 3, respectively. Compound 1 reacts with H2O in hydrocarbon solvents to give W2(O)4(μ-O)[W(η2-dmpe)2(CO)]2, 4. The compounds 1−4 contain unsupported W−W bonds between metal atoms in greatly different oxidation states. The new compounds have been characterized by NMR and infrared spectroscopy, and compounds 1 and 4, by single-crystal X-ray studies. For 1·0.5toluene at −171 °C, a = 19.546(3) Å, b = 21.745(4) Å, c = 18.114(3) Å, Z = 8, and space group Pcab and for 4·4CH2Cl2 at −169 °C, a = 13.282(2) Å, b = 14.308(3) Å, c = 15.319(3) Å, β = 97.88(1)°, Z = 2, and space group P21/n.
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