Chemistry of polynuclear metal complexes with bridging carbene or carbyne ligands. Part 54. Compounds derived from [W(CC6H4Me-4)(CO)2(η-C5Me5)] with bonds between tungsten and iron, cobalt, or nickel; crystal structure of [FeW{µ-C(C6H4Me-4)C(O)O}(CO)5(η-C5Me5)]

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Abstract
The compound [W(CC6H4Me-4)(CO)2(η-C5Me5)](1) reacts with [Fe(CO)3(η-C8H14)2] in hexane at ca.–50 °C to give predominantly the electronically unsaturated dimetal complex [FeW(µ-CC6H4Me-4)(CO)5(η-C5Me5)](2). With [Fe2(CO)9] in Et2O at ca. 10 °C, compound (1) yields a chromatographically separable mixture of (2), the saturated dimetal species [FeW(µ-CC6H4Me-4)(CO)6(η-C5Me5)], and the trimetal compound [Fe2W(µ3-CC6H4Me-4)(µ-CO)(CO)8(η-C5Me5)]. The latter is best obtained by treating (1) with excess of [Fe2(CO)9] in Et2O at ambient temperatures. Complex (2) reacts with oxygen and with sulphur to afford [FeW{µ-C(C6H4Me-4)C(O)O}(CO)5(η-C5Me5)](5) and [FeW(µ-SCC6H4Me-4)(CO)5(η-C5Me5)], respectively. The structure of (5) has been established by X-ray diffraction. The Fe–W bond [2.605(1)Å] is bridged by the C(C6H4Me-4)C(O)O fragment [Fe–O 2.007(3), W–O 2.128(3), Fe–C(C6H4Me-4) 2.054(4), and W–C(C6H4Me-4) 2.171(4)Å], with the CO group interacting weakly if at all with the iron or tungsten centres [Fe C(O) 2.380(3) and W C(O) 2.609(3)Å]. The iron atom carries three CO groups, and the tungsten two CO groups and the η-C5Me5 ligand. Treatment of (2) with an excess of CH2N2 gives [FeW{µ-C(C6H4Me-4)=CH2}(µ-CH2)(CO)5(η-C5Me5)]. However, with one equivalent of CH2N2, the major product is [FeW{µ-trans-CHC(H)C6H4Me-4}(µ-CO)(CO)5(η-C5Me5)], together with spectroscopically identified [FeW{µ-trans-CHC(H)C6H4Me-4}(µ-CH2)(CO)5(η-C5Me5)]. Compound (1) reacts with [Co2(CO)8] to give [Co2W(µ3-CC6H4Me-4)(CO)8(η-C5Me5)], and with [Ni2(µ-CO)2(η-C5H5)2] to give a mixture of [Ni2W(µ3-CC6H4Me-4)(CO)2(η-C5H5)2(η-C5Me5)] and [NiW2(µ-CC6H4Me-4)2(CO)4(η-C5Me5)2].

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