Chemistry of di- and tri-metal complexes with bridging carbene or carbyne ligands. Part 14. Triangulo-metal complexes containing tungsten with iron, cobalt, rhodium, or nickel and a capping tolylidyne ligand; crystal structure of the complex [RhFeW(µ3-CC6H4Me-4)(µ-CO)(CO)5(η-C5H5)(η-C9H7)]

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Abstract
Enneacarbonyldi-iron reacts at room temperature with the compounds [RhW(µ-CR)(CO)3(η-C5H5)-(η-C9H7)](R = C6H4Me-4) and [CoW(µ-CR)(CO)3(η-C5H5)(η-C5Me5)] to give the heteronuclear trimetallic complexes [RhFeW(µ3-CR)(µ-CO)(CO)5(η-C5H5)(η-C9H7)] and [CoFeW(µ3-CR)(µ-CO)(CO)5(η-C5H5)(η-C5Me5)], respectively. The structure of the rhodiumirontungsten compound was established by an X-ray diffraction study. Crystals are monoclinic, space group P21/c(no. 14), with Z= 4 in a unit cell of dimensions a= 9.018(2), b= 15.572(4), c= 18.503(6)Å, β= 103.69(2)°. Intensities were measured at room temperature to 2θ= 50°, and the structure has been refined to R 0.032 (R′ 0.034) for 3 497 unique reflections. The metal triangle has separations Fe–Rh 2.583(1), Fe–W 2.772(1), and Rh–W 2.760(1)Å, and is asymmetrically capped by the CC6H4Me-4 ligand [µ3-C–Fe 2.029(6), µ3-C–Rh 2.035(6), µ3-C–W 2.093(6)Å]. One CO ligand bridges the Fe–Rh bond, while the other five are terminally bonded; two to the tungsten, and three to the iron. The Rh–C(indenyl) distances suggest a tendency for η3 bonding of the ligand. The compound [RhW(µ-CR)(CO)3(η-C5H5)(η-C9H7)] reacts with [Rh(CO)2(η-C9H7)] in toluene at 60 °C to give [Rh2W(µ3-CR)(µ-CO)(CO)2(η-C5H5)(η-C9H7)2], and a related cluster [Rh2W(µ3-CR)(µ-CO)(CO)2(η-C5H5)(η-C5Me5)2] can be obtained from [Rh2(µ-CO)2(η-C5Me5)2] and [W(CR)(CO)2(η-C5H5)]. The latter reaction also affords the dimetal species [RhW(µ-CR)(CO)3(η-C5H5)(η-C5Me5)]. At 60 °C in toluene, [W(CR)(CO)2(η-C5H5)] and [Ni2(µ-CO)2(η-C5H5)2] give a mixture of the compounds [Ni2W(µ3-CR)(CO)2(η-C5H5)3] and [W2(µ-RC2R)(CO)4(η-C5H5)2]. The same products are obtained from [Ni(η-C5H5)2] and [W(CR)(CO)2(η-C5H5)], but the latter with [Ni2(µ-Me3SiC2SiMe3)(η-C5H5)2] affords [Ni2W(µ3-CR)(CO)2(η-C5H5)3] only. Pathways for the formation of some of the complexes, including [W2(µ-RC2R)(CO)4(η-C5H5)2], are proposed, and 1H and 13C n.m.r. data for the various species are reported.

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