Reactivity of Diynes with a 1-Azavinylidene-Bridged Triruthenium Carbonyl Cluster. Insertion Reactions of Diynes into Ru-H, Ru-C, and Ru-N Bonds Javier A. Cabeza,* ,† Fabrizia Grepioni,* ,‡ Marta Moreno, † and Vı ´ctor Riera † Departamento de Quı ´mica Orga ´ nica e Inorga ´ nica, Instituto de Quı ´mica Organometa ´ lica “Enrique Moles”, Universidad de Oviedo-CSIC, E-33071 Oviedo, Spain, and Dipartimento di Chimica, Universita ´ di Sassari, Via Vienna 2, I-07100 Sassari, Italy Received June 26, 2000 The reactivity of the 1-azavinylidene cluster complex [Ru 3 (µ-H)(µ-NdCPh 2 )(CO) 10 ](1) with diynes has been studied. The nonconjugated diyne 1-trimethylsilyl-1,4-pentadiyne affords the binuclear ynenyl derivative [Ru 2 (µ-NdCPh 2 )(µ-η 2 -CH 2 dCCH 2 CtCSiMe 3 )(CO) 6 ](2), which results from cluster fragmentation and from the insertion of the terminal alkyne fragment of the diyne into a Ru-H bond. The reactions of 1 with the internal conjugated diynes 1,6- diphenoxy-2,4-hexadiyne, 2,4-hexadiyne, and diphenylbutadiyne have allowed the isolation of the trinuclear derivatives [Ru 3 {µ-η 2 -NdCPh(C 6 H 4 )}(µ 3 -η 4 -PhOCH 2 CHdCdCdCHCH 2 OPh)- (CO) 8 ] (3), [Ru 3 {µ 3 -η 4 -NdCPh(C 6 H 4 )CH(Me)CHdCdCMe}(CO) 9 ] (4), [Ru 3 {µ-η 2 -NdCPh- (C 6 H 4 )}(µ 3 -η 4 -PhCHdCHCtCPh)(CO) 8 ](5), and [Ru 3 {µ 3 -η 4 -PhCHCHdC(CPh)NdCPh(C 6 H 4 )}- (CO) 9 ](6). The four compounds have been characterized by X-ray diffraction methods. They all arise from the orthometalation of a phenyl ring of the 1-azavinylidene ligand and from the transfer of two hydride ligands (the original plus that coming from the orthometalation) to the coordinated diyne. This hydrogenation process can proceed as a 1,4-addition to give a 1,2,3-triene fragment (as occurs in 3) or as a 1,2-addition to give an enyne fragment (as occurs in 5). In the cases of 4 and 6, a 1,2-addition of hydrogen is accompanied by the insertion of the unsaturated hydrocarbon fragment into the Ru-C bond associated with the orthometalated ring (4, 6) and into a Ru-N bond (6). The precise order by which these processes lead to the corresponding products has not been established. The reactions involved in the formation of compounds 2-6 represent excellent examples of insertion of diynes into M-H, M-C, and M-N bonds of metal clusters and have allowed the characterization of substituted 1-yn-3-enyl (in 2), 1,2,3-triene (in 3), 1,2-dienyl (in 4), 1-en-3-yne (in 5), and 2-(N-imido)-1,2,3-allyl-1-yl (in 6) ligands. Introduction The past decade has been witness to an increasing interest in the synthesis and reactivity of late-transi- tion-metal amido complexes as a consequence of the relative scarcity of such compounds 1-5 and of their potential use in C-N bond-forming reactions. 6-9 In this field, we have recently described a high-yield synthesis of [Ru 3 (µ-H)(µ-NdCPh 2 )(CO) 10 ](1), 5 a com- pound that contains a bridging amido ligand derived from benzophenone imine, which can be regarded as a 1-azavinylidene ligand. 10 As part of a general study of the reactivity of compound 1, 5-7,11 we have previously reported that the thermal reaction of 1 with an excess of diphenylacetylene results in the formation of the * Corresponding authors. J.A.C.: Fax: int + 34-985103446. E- mail: jac@sauron.quimica.uniovi.es. F.G.: Fax: int + 39-079212069. E-mail: grepioni@ssmain.uniss.it. † Universidad de Oviedo. ‡ Universita ` di Sassari. 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