Comparative reactivity of triruthenium and triosmium μ32-Imidoyls. 2. Reactions with alkynes

Shariff E. Kabir, Edward Rosenberg, Luciano Milone, Roberto Gobetto, Domenico Osella, Mauro Ravera, Timothy McPhillips, Michael W. Day, Douglas Carlot, Sharad Sharad, Erich Wolf, Kenneth Hardcastle

Risultato della ricerca: Contributo su rivistaArticolo in rivistapeer review

Abstract

The reactions of Ru3(CO)932-CH 3C=NCH2CH3)(μ-H) (1), M3(CO)932-C=N(CH 2)3)(μ-H) (M = Ru (2), M = Os (3)) with the alkynes RC≡CR (R = CH3, C6H5, CO2Me) have been studied. The ruthenium complexes 1 and 2 react with 2-butyne at 70 °C to give two very different trimetallic alkyne derivatives: Ru3(CO)7(μ-η24-C 4(CH3)4)(μ-η2-CH 3C=NCH2CH3)-(η1-COC(CH 3)C(H)CH3 (5) and Ru3(CO)832-C=N(CH 2)3)(μ-η2-CH3C(H)=CCH 3) (6). The osmium imidoyl 3 does not react with 2-butyne even at elevated temperatures. However, the reaction of Os3(CO)9(μ-η2-C=N(CH2) 3)(μ-H)(CH3CN) (7b), synthesized from Os3(CO)10-(μ-η2-C=N(CH2) 3)(μ-H) (7a), with 2-butyne yields the analog of 6, Os3(CO)832-C=N(CH 2)3)(μ-η2-RC(H)=CR) (R = CH3 (10), R = C6H5 (11)) on thermolysis of the initially formed nonacarbonyl precursors (8 and 9 for R = CH3), which are a mixture of isomers. Direct reaction of 7a with diphenylacetylene at 100 °C gives somewhat lower yields of 11. The reaction of 7b with dimethylacetylenedicarboxylate or the direct reaction of 3 with this alkyne yields the nonacarbonyl derivative Os3(CO)9(μ-η2-C=N(CH2) 3)(μ33-CH3O 2CC=C(H)CO2CH3) (12). Direct reaction of 7a with a 2.5 molar excess trimethylamine N-oxide at room temperature yields the alkyne-imidoyl-coupled product Os3(CO)8(μ-η6-CH 3C(H)=C(CH3)C-(CH3)=C(CH 3)C=N(CH2)3) (13). The solid state structures of 5, 11, 12, and 13 are reported. A comparative study of the electrochemical properties of 5 and 1 is also reported.

Lingua originaleInglese
pagine (da-a)2674-2681
Numero di pagine8
RivistaOrganometallics
Volume16
Numero di pubblicazione12
DOI
Stato di pubblicazionePubblicato - 1 gen 1997
Pubblicato esternamente

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