The formation and transformation of metallacycles containing phosphorus or sulfur on molybdenum- or tungsten-cobalt mixed-metal backbones

Jason D. King, Martin J. Mays, Giles E. Pateman, Paul R. Raithby, Moira A. Rennie, Gregory A. Solan, Nick Choi, Gráinne Conole, Mary McPartlin

Research output: Contribution to journalArticlepeer-review

19 Citations (SciVal)


The new heterobimetallic complexes of general formula [{(R′S)Ph2P}(OC)2Co{μ-C2(CO 2Me)2}M(η5-L)(CO)2] 1 [L = C5H5 or C5Me5; M = Mo or W; R′ = hydrocarbyl] undergo thermally induced phosphorus-sulfur bond breaking reactions. By variation of the nature of the R′ substituent, the cyclopentadienyl group or the Group 6 metal centre in 1, bimetallic complexes incorporating bridging four-membered metallacycles of the type M-P-C=C or M-S-C=C (where M = Co, Mo or W), are accessible. While [{(PhS)Ph2P}(OC)2Co{μ-C2(CO 2Me)2}Mo(η5-C5H 5)(CO)2] 1a gives as the sole product the phosphorus-containing molybdenacyclic species [(OC)(η5-C5H5)Mo{μ-PPh 2C(CO2Me)-C(CO2Me}(μ-SPh)Co(CO)2] 2a, the corresponding reaction of [{(R′S)Ph2P}(OC)2Co{μ-C2(CO 2Me)2}Mo(η5-C5H 5)-(CO)2] (R′ = Bun 1b; But 1c), results in the formation of both [(OC)(η5-C5H5)Mo{μ-PPh 2C(CO2Me)C(CO2Me)}-(μ-SR′)Co(CO) 2] (R′ = Bun 2b; But 2c) and [(OC)2Co{μ-SR′C(CO2Me)C(CO 2Me)}(μ-PPh2)Mo(η5-C5H 5)(CO)] (R′ = Bun 3b; But 3c). The latter sulfur-containing cobaltacyclic species (3c) has been shown to isomerise to the phosphorus-containing molybdenacyclic species 2c on further heating. Conversely, employment of the pentamethylcyclopentadienyl complex [{(PhS)Ph2P}(OC)2Co{μ-C2(CO 2Me)2}Mo(η5-C5Me 5)(CO)2] 1b gives three species, [(OC)(η5-C5Me5)Mo{μ-PPh 2C(CO2Me)C(CO2Me)}(μ-SPh)Co(CO)2] 2d and [(OC)2Co{μ-SPhC(CO2Me)C(CO 2Me)}-(μ-PPh2)Mo(η5-C5Me 5)(CO)] 3d, which are, respectively, analogues of 2a-3c and 3b, 3c, and in addition the phosphorus-containing cobaltacyclic species [(OC)2Co{μ-PPh2C(CO2Me)C(CO 2Me)}(μ-SPh)Mo(η5-C5Me5)(CO)] 4d. Thermolysis of [{(BunS)Ph2P}(OC)2Co{μ-C2(CO 2Me)2}W(η5-C5H 5)(CO)2] 1e, in which a tungsten centre has been introduced in place of the molybdenum in 1b, affords only sulfur-containing metallacyclic products, which incorporate either the cobalt centre as in [(OC)2Co{μ-SBunC(CO2Me)C(CO 2Me)}(μ-PPh2)W(η5-C5H 5)(CO)] 3e or the tungsten centre as in [(OC)(η5-C5H5)W{μ-SBu nC(CO2Me)C(CO2Me)}(μ-PPh 2)Co(CO)2] 5e. The 'flyover' complex [(OC)(η5-C5H5)W{μ-C(CO 2Me)CHC(OMe)O}(μ-SPh)Co(CO){PPh2(SPh)}] 6 was the only product obtained from the reaction of [(OC)3Co{μ-C2(CO2Me) 2}W(η5-C5H5)(CO)2] with Ph2P(SPh). Single crystal X-ray diffraction studies have been performed on complexes 1d, 2b, 3c′ [the P(OMe)3-substituted derivative of 3c], 5e and 6.

Original languageEnglish
Pages (from-to)4447-4456
Number of pages10
JournalJournal of the Chemical Society - Dalton Transactions
Issue number24
Publication statusPublished - 21 Dec 1999

ASJC Scopus subject areas

  • General Chemistry


Dive into the research topics of 'The formation and transformation of metallacycles containing phosphorus or sulfur on molybdenum- or tungsten-cobalt mixed-metal backbones'. Together they form a unique fingerprint.

Cite this