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Comparative properties of fluorous phosphine ligand complexes: W(CO)5L. Crystal structure of W(CO)5P(C6H4-4-CH2CH2(CF2)7CF3)3 |
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| Authors: | Thomas J Malosh Scott R Wilson |
| Institution: | a Department of Chemistry, University of Pittsburgh at Johnstown, 450 Schoolhouse Road, Johnstown, Pennyslvania 15963, United States b George L. Clark X-Ray Facility, University of Illinois at Urbana-Champaign, United States c Department of Chemistry, University of Illinois at Urbana-Champaign, United States |
| Abstract: | The compounds W(CO)5P(C6H4-4-CH2CH2(CF2)7CF3)3 (1) and W(CO)5P(CH2CH2(CF2)5CF3)3 (2) were synthesized in order to probe the electronic and physical effects of ligation by perfluorocarbon substituted tertiary phosphine ligands in a W(CO)5L complex. The π-accepting ability of the fluorous phosphines was found to rank with non-fluorous comparators as P(CH2CH2(CF2)5CF3)3 > P(C6H4-4-CH2CH2(CF2)7CF3)3 > PPh3 > P(p-tolyl)3 > P(n-octyl)3. The X-ray crystal structure of W(CO)5P(C6H4-4-CH2CH2(CF2)7CF3)3 shows strong intermolecular association of fluorous components but confirms that the para fluorocarbon subtituents have an insignificant effect on the tungsten coordination environment. Partition coefficients (toluene/perfluoromethylcyclohexane) were measured for compounds 1 and 2. |
| Keywords: | Fluoroponytail phosphine Fluorous soluble phosphine W(0) phosphine complex Fluorous biphasic system Fluorous biphasic separation Fluorous partition coefficient |
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