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Investigation of the dithiocarbamate-induced coupling of allylidene and carbonyl ligands on a tungsten center |
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| Authors: | Marianna F. Asaroa Andreas Mayr Bart Kahra Donna Van Engen |
| Affiliation: | a Department of Chemistry, Princeton University, Princeton, NJ 08544 USA b Department of Chemistry, State University of New York at Stony Brook, Stony Brook, NY 11794-3400 USA |
| Abstract: | Reaction of the allylidene tungsten complex [W(CPhCHCHMe)Br2(CO)2(4-picoline)] (1) with the dithiocarbamates MS2CNR2 (a: M=Na, R=Et; b: M=Na, R=Me; c: M=Li, R=Ph) in THF at 50 °C affords the vinylketene tungsten complexes [W(S2CNR2)2(OCCPhCHCHMe)(CO)] (2a–c). At lower temperatures, four reaction intermediates (3–6) may be discerned. Spectroscopic studies indicate that these compounds contain η4-allyldithiocarbamate ligands which are generated by addition of dithiocarbamate across the metal-carbon double bond of the allylidene-tungsten unit in 1. The structures of [W(S2CNEt2)2(OCCPhCHCHMe)(CO)] (2a) and of one intermediate, [W(η4-Et2NCS2CPhCHCHMe)(S2CNEt2)(CO)2] (5a) were elucidated by X-ray crystallography. |
| Keywords: | Coupling reaction Dithiocarbamate ligand Tungsten complexes Carbonyl complexes Alkylidene complexes |
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