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

Javier A. Cabeza, Marina Damonte, Pablo Garcia-Alvarez, Alan Kennedy, Enrique Perez-Carreno

Research output: Contribution to journalArticle

39 Citations (Scopus)

Abstract

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.

Original languageEnglish
Pages (from-to)826-833
Number of pages8
JournalOrganometallics
Volume30
Issue number4
DOIs
Publication statusPublished - 28 Feb 2011

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phosphine
Carbon Monoxide
imidazoles
phosphines
reactivity
Salts
salts
ligands
Ligands
carbenes
Derivatives
Deprotonation
fragments

Keywords

  • n- heterocyclic-carbene
  • carbonyl clusters
  • ray crystal-structures
  • methyl-group
  • catalytic applications
  • structural-characterization
  • stereodirecting ligands
  • asymmetric catalysis

Cite this

Cabeza, Javier A. ; Damonte, Marina ; Garcia-Alvarez, Pablo ; Kennedy, Alan ; Perez-Carreno, Enrique. / Reactivity of [Ru-3(CO)(12)] with a phosphine-functionalized Imidazol-2-ylidene and Its imidazolium salt. In: Organometallics. 2011 ; Vol. 30, No. 4. pp. 826-833.
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abstract = "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.",
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Reactivity of [Ru-3(CO)(12)] with a phosphine-functionalized Imidazol-2-ylidene and Its imidazolium salt. / Cabeza, Javier A.; Damonte, Marina; Garcia-Alvarez, Pablo; Kennedy, Alan; Perez-Carreno, Enrique.

In: Organometallics, Vol. 30, No. 4, 28.02.2011, p. 826-833.

Research output: Contribution to journalArticle

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T1 - Reactivity of [Ru-3(CO)(12)] with a phosphine-functionalized Imidazol-2-ylidene and Its imidazolium salt

AU - Cabeza, Javier A.

AU - Damonte, Marina

AU - Garcia-Alvarez, Pablo

AU - Kennedy, Alan

AU - Perez-Carreno, Enrique

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N2 - 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.

AB - 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.

KW - n- heterocyclic-carbene

KW - carbonyl clusters

KW - ray crystal-structures

KW - methyl-group

KW - catalytic applications

KW - structural-characterization

KW - stereodirecting ligands

KW - asymmetric catalysis

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