Two modes of C–H bond activation of tris(2-thienyl)phosphine in trinuclear osmium carbonyl clusters

Reaction of [Ru3(CO)12] with tri(2-furyl)phosphine: Di- and tri-substituted triruthenium and phosphido-bridged diruthenium complexes

“…Reaction of 3 with excess DMAD in refluxing toluene for 4 h gives a pale yellow solution that, upon separation by TLC, affords C 6 (CO 2 Me) 6 in addition to some unconsumed 3. The cyclotrimerization product has been characterized by 1 H, 13 C NMR spectroscopy and elemental analysis, the former corresponding to data reported by Thomas and Darkwa [45].…”

“…This transformation is accompanied by dissociation of carbonyl in order to keep the closed triruthenium framework. We have recently reported a similar bonding mode of the l-g 1 ,g 1 12 with tri(2-thienyl)phosphine at 110°C [13]. To the best of our knowledge, this type of furyl cyclometallation at a trimetallic framework is unprecedented in the literature.…”

“…More recently, the reactivity of group 8 metal carbonyls with functionalized phosphines such as diphenyl(2-thienyl)phosphine [8][9][10][11], di(2-thienyl)phenylphosphine [12], diphenyl(benzothienyl)phosphine [12], tri(2-thienyl)phosphine [13][14][15], diphenyl(2-pyridyl)phosphine [16][17][18][19][20][21] and 2-indolyl phosphine [22] have attracted considerable attention since the presence of a second coordinating atom provides a diversity of coordination modes. It is well-documented that heterodifunctional ligands exhibit very interesting properties, such as selective binding to metal ions of different types, dynamic behavior via reversible dissociation of the weaker metal-ligand bond and stereoelectronic control of the coordination sphere of the metal [23].…”

Carbon-Hydrogen Bond Activation of Phenyldi(2- Thienyl)Phosphine at A Triruthenium Cluster Center

“…[5][6][7][8][9][10][11][12][13][14][15][16][17] In this context, the reactivity of thienylphosphines with triosmium and triruthenium clusters has been thoroughly examined in recent years. [10][11][12][13][14][15][16][17] The first report in this area was by Vahrenkamp et al in 1995 who documented the reaction of Ru 3 (CO) 12 with tri(2-thienyl)phosphine from which two simple tertiary phosphine substituted products [Ru 3 (CO) 10 12 and we demonstrated the reactivity of tri(2-thienyl)phosphine with [Ru 3 (CO) 10 (µ-dppm)] {dppm = bis(diphenylphosphino)methane}. [11][12] A worth of interesting reactivity pattern and structural features were obtained from those studies such as carbon-hydrogen and carbonphosphorous bond cleavage leading to cyclometalated µ 3 -R 2 P(C 4 H 2 S) (R = Ph, Th) and µ 4 -thiophyne ligands as well as carbon-sulfur bond cleavage leading to thiophene ring opening required for desulfurization.…”

“…The reactions of thienylphosphines with triosmium clusters also lead to the formation of both simple substitution and metalated product which were demonstrated by Nordlander and our research group. [13][14][15] As part of our work on the reactivity of thienylphosphines with trimetallic clusters, we have studied the reactivity of phenyldi(2-thienyl)phosphine (PhPTh 2 ) with Ru 3 (CO) 12 , the results of which are described herein.…”