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Reactivity of [Ru-3(CO)(12)] with a phosphine-functionalized Imidazol-2-ylidene and Its imidazolium salt

Cabeza, Javier A. and Damonte, Marina and Garcia-Alvarez, Pablo and Kennedy, Alan and Perez-Carreno, Enrique (2011) Reactivity of [Ru-3(CO)(12)] with a phosphine-functionalized Imidazol-2-ylidene and Its imidazolium salt. Organometallics, 30 (4). pp. 826-833. ISSN 0276-7333

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The trinuclear cluster [Ru-3(CO)(12)] reacts at room temperature with the phosphine-functionalized N-heterocyclic carbene (NHC) ligand 1[2-(diphenylphophino)ethyl]-3-methylimidazol-2-ylidene (dppeImMe), in 1:1 mol ratio, to give the edge-bridged trinuclear derivative [Ru-3(mu-kappa C-2,P-dppeImMe)(CO)(10)] (1). The use of a 1:3 [Ru-3(CO)(12)] to dppeImMe mol ratio leads to the mononuclear derivative [Ru(kappa C-2,P-dppeImMe)(CO)(3)] (2), which has a trigonal-bipyramidal ligand arrangement with the NHC and phosphine fragments of the dppeImMe ligand in axial and equatorial positions, respectively. Upon gentle heating (refluxing. THF), compound 1 is transformed into the face-capped dihydrido derivative [Ru-3(mu-H)(2)(mu(3)-kappa C-3(2),P-dppeImCH)(CO)(8)] (3), which arises from the oxidative addition of two C-H bonds of the N-methyl group of the dppeImMe ligand. The trinuclear salt [Ru-3(kappa P-dppeHImMe)(3)(CO)(9)][BF4](3) (4[BF4](3)), which contains a P-coordinated 1[2-(diphenylphophino)ethy1]-3-methylimidazolium ligand ([dppeHImMe](+)) on each Ru atom, has been prepared by treating [Ru-3(CO)(12)] with the salt [dppeHImMe][BF4]. The deprotonation of 4[BF4](3) with three equivalents of K[N(SiMe3)(2)] is an alternative way to prepare the mononuclear complex 2.