163591-51-3Relevant academic research and scientific papers
Dicarbonyl and tricarbonyl adducts of (W≡W)6+--containing complexes. Preparation and structures of W2(OCMe2CF3)6(CO)2 and W2(OCMe(CF3)2)4(NMe 2)2(CO)3
Budzichowski, Theodore A.,Chisholm, Malcolm H.,Tiedtke, Darin B.,Huffman, John C.,Streib, William E.
, p. 2318 - 2324 (2008/10/09)
Carbon monoxide adds reversibly to W2(OR)6 compounds to give W2(OR)6(CO)2 complexes (R = SitBuMe2, 1; CMe2CF3, 2; 2,6-Me2C6H3, 3) wherein the CO ligands bond to alternate tungsten atoms in a manner that allows mixing of WW π and W dπ to CO π* bonding. In contrast to the homoleptic alkoxides above, the mixed amido-alkoxide complex W2(OCMe-(CF3)2)4(NMe 2)2 (4), which also takes up 2 equiv of CO, reacts further to give W2(OCMe-(CF3)2)4(NMe 2)2(CO)3 (6), which has an unusual structure wherein three CO ligands are bonded to a single tungsten atom and the W-W bond is supported by one NMe2 bridge. The formation of 6 is also reversible. 2 and 6 have been characterized by single-crystal X-ray crystallography, and all compounds have been characterized by 1H and 13C{1H} NMR spectroscopy. The results are compared to earlier studies of the addition of CO to M2(OR)6 complexes such as W2(OtBu)6, which give bridged monocarbonyl adducts, and that of Wolczanski et al. (Miller, R. L.; Wolczanski, P. T.; Rheingold, A. L. J. Am. Chem. Soc. 1993, 115, 10422) wherein CO and W2Cl2(silox)4 (silox = tBu3SiO) react reversibly to give a bis-(carbonyl) adduct with subsequent cleavage to give (silox)2(O)W(μ-C)W(silox)2Cl2. For 2, C26H36F18O8W2, FW = 1186.2; a = 11.256(4), b = 18.496(6), c = 17.789(7) A?; β = 97.97(1)°; monoclinic P21/n, Z = 4. For 6, C23H24F24N2O7W 2, FW = 1264.1; a = 14.053(3), b = 21.148(5), c = 12.789(3) A?; α = 106.11(1), β = 103.15(1), γ = 86.81(1)°; triclinic P1, Z = 4.
