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DOI: 10.1039/A906607A (Paper) Reference Section for: J. Chem. Soc., Dalton Trans., 1999, 4447-4456

The formation and transformation of metallacycles containing phosphorus or sulfur on molybdenum– or tungsten–cobalt mixed-metal backbones[hair space]‡

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

Abstract

The new heterobimetallic complexes of general formula [{(R′S)Ph2P}(OC)2Co{µ-C2(CO2Me)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[double bond, length half m-dash]C or M–S–C[double bond, length half m-dash]C (where M = Co, Mo or W), are accessible. While [{(PhS)Ph2P}(OC)2Co{µ-C2(CO2Me)2}Mo(η5-C5H5)(CO)2] 1a gives as the sole product the phosphorus-containing molybdenacyclic species [(OC)(η5-C5H5)Mo{µ-PPh2C(CO2Me)C(CO2Me}(µ-SPh)Co(CO)2] 2a, the corresponding reaction of [{(R′S)Ph2P}(OC)2Co{µ-C2(CO2Me)2}Mo(η5-C5H5)(CO)2] (R′ = Bun 1b; But 1c), results in the formation of both [(OC)(η5-C5H5)Mo{µ-PPh2C(CO2Me)C(CO2Me)}(µ-SR′)Co(CO)2] (R′ = Bun 2b; But 2c) and [(OC)2Co{µ-SR′C(CO2Me)C(CO2Me)}(µ-PPh2)Mo(η5-C5H5)(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(CO2Me)2}Mo(η5-C5Me5)(CO)2] 1b gives three species, [(OC)(η5-C5Me5)Mo{µ-PPh2C(CO2Me)C(CO2Me)}(µ-SPh)Co(CO)2] 2d and [(OC)2Co{µ-SPhC(CO2Me)C(CO2Me)}(µ-PPh2)Mo(η5-C5Me5)(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(CO2Me)}(µ-SPh)Mo(η5-C5Me5)(CO)] 4d. Thermolysis of [{(BunS)Ph2P}(OC)2Co{µ-C2(CO2Me)2}W(η5-C5H5)(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(CO2Me)}(µ-PPh2)W(η5-C5H5)(CO)] 3e or the tungsten centre as in [(OC)(η5-C5H5)W{µ-SBunC(CO2Me)C(CO2Me)}(µ-PPh2)Co(CO)2] 5e. The ‘flyover’ complex [(OC)(η5-C5H5)W{µ-C(CO2Me)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.

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