The molybdenum-molybdenum triple bond—XVII. Syntheses,spectroscopic and structural characterizations of Mo4F4(O—t-Bu)8 and Mo2F2(O—t-Bu)4(PMe3)2 (MoMo) |
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Authors: | Malcolm H. Chisholm David L. Clark John C. Huffman |
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Affiliation: | Department of Chemistry and Molecular Structure Center, Indiana University, Bloomington, IN 47405, U.S.A. |
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Abstract: | Hydrocarbon solutions of Mo2(O—t-Bu)6 and PF3 (2 equiv) yield Mo4F4(O—t-Bu)8, I, and PF2(O—t-Bu). Compound I contains a bisphenoid of molybdenum atoms with two short MoMo distances, 2.26 Å, and four long MoMo distances, 3.75 Å, corresponding to localized MoMo triple bonding and non-bonding distances, respectively. The tetranuclear compound may be viewed as a dimer, [Mo2(μ2-F)2(O-t-Bu)4]2, and addition of PMe3 to hydrocarbon solutions of I yields Mo2F2(O—t-Bu)4(PMe3)2, II, which contains an unbridged MoMo triple bond of distance 2.27 Å. Each molybdenum atom is coordinated to two oxygen atoms, one fluorine atom and the phosphorus atom of the PMe3 ligand in a roughly square planar manner. The overall central Mo2O4F2P2 skeleton has C2 symmetry and NMR studies (1H, 19F and 31P) are consistent with the maintenance of this type of structure in solution. Infrared and electronic absorption spectral data are reported. These are the first compounds containing fluorine ligands attached to the (MoMo)6+ unit. |
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Keywords: | Author to whom correspondence should be addressed. |
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