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Chemistry of Polynuclear Metal Complexes with Bridging Carbene or Carbyne Ligands. Part 65. Reactions of the Complexes and 3-CR)(μ-CO)(CO)8(η-C5Me5)> (R=C6H4Me-4) with Alkynes R'C2R' (R'= Me or Ph); Crystal Structures of

DOI: 10.1039/DT9870002211

Source and publish data:

Journal of the Chemical Society, Dalton Transactions p. 2211 - 2218 (1987)

Update date:2022-08-05

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Authors:

Hein, JoachimHein, Joachim

Jeffery, C. JohnJeffery, C. John

Sherwood, PaulSherwood, Paul

Stone, F. Gordon A.Stone, F. Gordon A.

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Article abstract of DOI:10.1039/DT9870002211

The compounds and 3-CC6H4Me-4)(μ-CO)(CO)8(η-C5Me5)> react with PhC<*>CPh in toluene at ca. 85 deg C to afford the complex (CO)5(η-C5Me5)>.Similarly, the di-iron-tungsten compound and MeC<*>CMe afford the related species (CO)5(η-C5Me5)>.In contrast, the dimetal compound and MeC<*>CMe under mild conditions (ca. 0 deg C, in Et2O) yield a mixture of the two complexes (CO)5(η-C5Me5)> (ca. 50-60percent) and (μ-CO)(CO)3(η-C5Me5)> (ca. 5-10percent).The structures of both these products have been established by X-ray diffraction studies.In the former the Fe-W bond <2.722(1) Angstroem> is transversely bridged by a μ-C(C6H4Me-4)C(O)C(Me)C(Me) group, with the end carbon atoms of the chain ?-bonded to the tungsten, and the iron attached to the three carbon atoms carrying the two methyl and the tolyl substituents.The ketonic carbonyl group is at a non-bonding distance from both metal centres.The minor reaction product has an Fe-W bond <2.729(1) Angstroem> brigded by a carbonyl group, the other three carbonyl groups being terminally bound to the iron.The iron atom is part of a FeC(C6H4Me-4)C(Et)C(H)C(Me)C(Me) metallacycle, with all the atoms of this six-membered ring being attached to the tungsten atom which is also ligated by the η-C5Me5 group.The (1)H and (13)C-<(1)H> n.m.r. data of the new compounds are reported and discussed.

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