Skip to Main content Skip to Navigation
Journal articles

Reactions of dinuclear and polynuclear complexes XIX. Rearrangements of terminal or disubstituted alkyne ligands present in homo- and heterodinuclear complexes of cobalt and molybdenum during reactions with molybdenum and cobalt carbonyl compounds: Formation of trinuclear and tetranuclear clusters

Abstract : The dicobalt alkyne complex [Co2(μ-PhC≢CH)(CO)6] 1a reacted with [Mo2(η5-C5H5)2CO)4] in refluxing tetrahydrofuran (THF) to give the μ3-alkylidyne trinuclear cluster [Co2Mo(η5-C5H5)(μ3 -CCH2Ph)(CO)8] 3 as the major product. Possible routes to the formation of 3 have been investigated. Among the identified minor products from this reaction were [CoMo2(η5-C5H5)2(μ 3-CCH2Ph)(CO)7] 4, [Co2Mo2(η5-C5H5)2(μ4-PhC2H)(μ-CO)4(CO)4] 5 and [Co3Mo(η5-C5H5)2(μ 4-PhC2H)(μ-CO)2(CO)5] 6. In contrast, when the related dicobalt complexes [Co2(μ-CF3C≢CR) (CO)6] (R=CF3 (1b), H (1c)), which contain alkynes with more strongly electron-withdrawing substituents, were heated with [Mo2(η5-C5H5)2(CO)4] in THF only mixed-dinuclear complexes [(η5-C5H5)(CO)2Mo(μ-CF3C2R)Co(CO)3](Mo-Co) (R=H (7a), CF3 (7b)) were formed. The reaction of the mixed-dinuclear complex 7b with [Co(η5-C5H5)(CO)2] led to the mixed-tetranuclear butterfly cluster [Co2Mo2(η5-C5H5)3(μ-CO)(CO)3] 8. The thermal reaction of 1b with the phosphido compound [Mo2(η5-C5H5)2(μ-C O)(μ-PPh2)2] gave rise to a single product, [Mo2(η5-C5H5)2(μ-P Ph2)_μ-PPh2Co2(μ-CF3C2CF3)(CO)5₍CO)2] 9, in which a phenyl ring of the (μ-phosphido)dimolybdenum moiety is π-bonded to one of the two cobalt atoms. Spectroscopic data for the new complexes are discussed.
Document type :
Journal articles
Complete list of metadatas

https://hal.univ-brest.fr/hal-01770716
Contributor : Nicolas Renard <>
Submitted on : Thursday, April 19, 2018 - 10:57:56 AM
Last modification on : Thursday, October 3, 2019 - 8:50:02 AM

Links full text

Identifiers

Collections

Citation

R. Rumin, P. Abiven, François Pétillon, K.W. Muir. Reactions of dinuclear and polynuclear complexes XIX. Rearrangements of terminal or disubstituted alkyne ligands present in homo- and heterodinuclear complexes of cobalt and molybdenum during reactions with molybdenum and cobalt carbonyl compounds: Formation of trinuclear and tetranuclear clusters. Journal of Organometallic Chemistry, Elsevier, 1998, 555, pp.89--100. ⟨10.1016/S0022-328X(97)00688-8⟩. ⟨hal-01770716⟩

Share

Metrics

Record views

115