Reactivity of Fe3and Ru3μ3-Phenylimido Clusters with Alkynes, Aliene, and 1,3-Cyclohexadiene

Jeong Sup Song, Sung Hwan Han, Sonbinh T. Nguyen, Gregory L. Geoffroy*, Arnold L. Rheingold

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

51 Scopus citations

Abstract

The reactivity of alkynes with the imido clusters Ru33-NPh)2(CO)9, H2Ru33-NPh)(CO)9, Fe33-NPh)(CO)10, Fe33-NPh)2(CO)9, and H2Fe33-NPh)(CO)9has been examined. The cluster Fe23-NPh)(CO)10reacts regiospecifically with a series of alkynes to form the binuclear ferrapyrrolinone complexes Fe223-RC=C(R’)C(O)NPh)(CO)6, possessing a metallacycle formed by coupling of the alkyne with CO and the imido ligand. These same ferrapyrrolinone complexes also form when H2Fe33-NPh)(CO)9is allowed to react with PhC≡CPh, EtC≡CEt, and PhC≡CMe. The derivative formed from PhC≡CMe was found to undergo subsequent substitution of one CO ligand by But≡C to form Fe223-PhC=C(Me)C(O)-NPh)(CO)5(CNBut), which was crystallographically characterized. The bis(imido) cluster Ru33-NPh)2(CO)9reacts with PhC≡CPh to form the tetranuclear cluster Ru43-NPh)222-PhC≡CPh)(CO)10, which has been crystallographically shown to possess a butterfly arrangement of the four ruthenium atoms with the alkyne bridging the hinge of the butterfly in a perpendicular fashion and with the imido ligands bridging the open triangular faces of the butterfly. The analogous triiron cluster Fe33-NPh)2(CO)9reacts with PhC≡CPh to give a mixture of products, from which the ferracyclopentadiene Fe224-PhC=C(Ph)C-(Ph)=CPh)(CO)6and the binuclear ferraazetine complex Fe223-PhC=C(Ph)NPh)(CO)6were characterized. The latter compound possesses a four-membered metallacycle formed by coupling of the alkyne with the imido ligand. Treatment of H2Ru33-NPh)(CO)9with PhC≡CPh results in the formation of the cluster Ru44-NPh)(μ42-PhC≡CPh)(CO)11, which has been crystallographically shown to possess a planar arrangement of the four ruthenium atoms bridged on one side by the μ4-imido ligand and the other by the alkyne. The cluster Fe33-NPh)(CO)10has also been found to react with 1,3-cyclohexadiene and with aliene to respectively form the trinuclear clusters Fe33-NPh)(CO)84-1,3-cyclohexadiene) and Fe33-NPh)(CO)826-C6H8). Crystallographic characterization has shown that in the former the diene has replaced two CO's and is coordinated to a single iron atom whereas in the latter two alienes have coupled through their central carbon atoms to form a C6H8ligand that bridges two iron atoms with each C3H4unit of the ligand η3-bonded to a single iron.

Original languageEnglish (US)
Pages (from-to)2386-2395
Number of pages10
JournalOrganometallics
Volume9
Issue number8
DOIs
StatePublished - Jan 1 1990

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Organic Chemistry
  • Inorganic Chemistry

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