Reaction of Fe(CO)2(η2-CS2){P(OR)3}2 with phosphines: desulphurization versus substitution. Crystal structures of Fe(CO)2(CS){P(OPh)3}2 and Fe(CO)3{P(OPh)3}2
| Autor: | Patrick McArdle, J. Renze, M. Barrow, Desmond Cunningham, Anthony R. Manning, Natalie L. Cromhout |
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| Rok vydání: | 1998 |
| Předmět: |
Trigonal planar molecular geometry
Stereochemistry Ligand Organic Chemistry Crystal structure Biochemistry Inorganic Chemistry Solvent chemistry.chemical_compound Trigonal bipyramidal molecular geometry Crystallography chemistry Materials Chemistry Physical and Theoretical Chemistry Benzene Acetonitrile Dichloromethane |
| Zdroj: | Journal of Organometallic Chemistry. 563:201-207 |
| ISSN: | 0022-328X |
| DOI: | 10.1016/s0022-328x(98)00575-0 |
| Popis: | The reaction of Fe(CO)2(η2-CS2){P(OPh)3}2 1 with two equivalents of PBu3 in a minimum volume of a polar solvent such as acetonitrile or dimethylsulfoxide afforded the thiocarbonyl derivative Fe(CO)2(CS){P(OPh)3}2 2 in ca. 80% yield whereas reaction in solvents such as dichloromethane or benzene afforded the substitution products Fe(CO)2(η2-CS2){P(OPh)3}(PBu3) and Fe(CO)2(η2-CS2)(PBu3)2. Although desulphurization of Fe(CO)2(η2-CS2){P(OR)3}2 by PBu3 in polar solvents is not a general route to Fe(CO)2(CS){P(OR)3}2 for all R, the new compound Fe(CO)2(CS){P(OEt)3}2 has been obtained and characterised spectroscopically. The crystal structures of 2 and Fe(CO)3{P(OPh)3}2 were determined and are very similar. Both compounds are trigonal bipyramidal about the Fe atom with trans apical phosphite ligands and a trigonal planar arrangement of CO/CS groups. The CS ligand in 2 was found to be disordered over two sites with occupancies 0.63 and 0.37. |
| Databáze: | OpenAIRE |
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