Unprecedented coupling of vinylidene and allenylidene ligands with dithiocarbamates: X-ray structure of [Ru{C(CCPh2)SC(NMe2)S}(S2CNMe2)(CO)(PPh3)]
| Autor: | Andrew J. P. White, Karsten J. Harlow, Darren J. Cook, Beatrice Buriez, Tom Welton, David J. Williams, Anthony F. Hill, James D. E. T. Wilton-Ely |
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| Rok vydání: | 1999 |
| Předmět: |
chemistry.chemical_classification
Stereochemistry Organic Chemistry X-ray chemistry.chemical_element Protonation Metallacycle Coupling (probability) Biochemistry Medicinal chemistry Toluene Ruthenium Inorganic Chemistry Silver salts chemistry.chemical_compound chemistry Materials Chemistry Physical and Theoretical Chemistry Dithiocarbamate |
| Zdroj: | Journal of Organometallic Chemistry. 578:264-267 |
| ISSN: | 0022-328X |
| Popis: | The reaction of [RuCl(PPh3)2{HB(pz)3}] (pz=pyrazol-1-yl) with 4-ethynyl toluene provides [RuCl(CCHC6H4Me-4)(PPh3){HB(pz)3}] (1a) which reacts with [Et2NH2][S2CNEt2] to give the metallacyclic alkenyl complex [Ru{C(CHC6H4Me-4)SC(NEt2)S}(PPh3){HB(pz)3}] (2). The reaction of [RuCl(PPh3)2{HB(pz)3}] with diphenylpropynol and Ag[PF6] however provides [Ru(CCCPh2)(PPh3)2{HB(pz)3}]PF6 (3) or in the absence of silver salts, the neutral complex [RuCl(CCCPh2)(PPh3){HB(pz)3}] (4). Both (3) and (4) react with Na[S2CNMe2] to give the metallacyclic allenyl complex [Ru{C(CCPh2)SC(NMe2)S}(PPh3){HB(pz)3}] (5). Treatment of [RuHCl(CO)(PPh3)3] with diphenylpropynol and Na[S2CNMe2] provides [Ru(CHCHCPh2OH)(S2CNMe2)(CO)(PPh3)2] which reacts with excess diphenylpropynol to give the alkynyl complex [Ru(CCCPh2OH)(S2CNMe2)(CO)(PPh3)2]. Protonation of this complex with HBF4 provides the allenylidene complex [Ru(CCCPh2)(S2CNMe2)(CO)(PPh3)2]BF4 (6) which reacts with Na[S2CNMe2] to give a kinetic isomer (7k) and ultimately a structurally characterised thermodynamic isomer of the metallacyclic allenyl complex [Ru{C(CCPh2)SC(NMe2)S}(S2CNMe2)(CO)(PPh3)] (7t). |
| Databáze: | OpenAIRE |
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