Phosphorus–carbon bond cleavage of Ph2PCH2PPh2 at a triruthenium center: synthesis and structural characterization of [Ru3(μ-CO)(CO)6(μ-PPh2)2(μ3-CH2PPh)]

Dppm-substituted ruthenium clusters with capping sulfido and selenido ligands derived from thiourea, tetramethylthiourea and elemental selenium

“…Naturally, we wished to compare such reactivity patterns for osmium with that of the ruthenium analogue 4, which has also attracted attention for its reactivity with various small organics and for the role of dppm in stabilizing the cluster [16][17][18][19][20][21][22][23][24][25][26][27]. In this context, we describe in this paper the reactions of 4 with tetramethylthiourea, thiourea and elemental selenium.…”

P–C and C–H bond cleavages of dppm in the thermal reaction of [Ru3(CO)10(μ-dppm)] with benzothiophene: X-ray structures of [Ru6(μ-CO)(CO)13{μ4-PhP(C6H4)PPh}(μ6-C)] and [Ru4(CO)9(μ3-η2-PhPCH2PPh2)(μ4-η6:η1:η1-C6H4)(μ-H)]

“…Recently, García et al demonstrated that [Ru 3 (CO) 12 ] reacts with dibenzothiophene at 98°C to give the dinuclear complex [Ru 2 (C 12 H 8 )(CO) 5 (l-CO)], by a double C-S bond activation-desulfurization process [6]. The lightly stabilized osmium cluster [Os 3 -(CO) 10 (MeCN) 2 ] reacts with thiophene and benzothiophene to give a series of Os-thiophene complexes in which the thiophene has undergone bond cleavage to give C-S and C-H bond activated products. For example, [Os 3 (CO) 10 -(MeCN) 2 ] reacts with benzothiophene at ambient temperature to give [Os 3 (CO) 10 (l-C 8 H 5 S)(l-H)] and [Os 3 (CO) 9 (l 3 -C 8 H 4 S)(l-H) 2 ]; whereas, at elevated temperature (80°C) an additional ring-cleaved complex, [Os 3 (CO) 10 (l-C 8 H 6 S)], is also obtained [2,5].…”

“…The lightly stabilized osmium cluster [Os 3 -(CO) 10 (MeCN) 2 ] reacts with thiophene and benzothiophene to give a series of Os-thiophene complexes in which the thiophene has undergone bond cleavage to give C-S and C-H bond activated products. For example, [Os 3 (CO) 10 -(MeCN) 2 ] reacts with benzothiophene at ambient temperature to give [Os 3 (CO) 10 (l-C 8 H 5 S)(l-H)] and [Os 3 (CO) 9 (l 3 -C 8 H 4 S)(l-H) 2 ]; whereas, at elevated temperature (80°C) an additional ring-cleaved complex, [Os 3 (CO) 10 (l-C 8 H 6 S)], is also obtained [2,5]. Arce et al have reported that [Os 3 (CO) 10 (MeCN) 2 ] reacts with dibenzothiophene in refluxing cyclohexane to affords only one product, the nonacarbonyl species [Os 3 (CO) 9 (l 3 -C 12 H 6 S)(l-H) 2 ] [3].…”

“…For example, [Os 3 (CO) 10 -(MeCN) 2 ] reacts with benzothiophene at ambient temperature to give [Os 3 (CO) 10 (l-C 8 H 5 S)(l-H)] and [Os 3 (CO) 9 (l 3 -C 8 H 4 S)(l-H) 2 ]; whereas, at elevated temperature (80°C) an additional ring-cleaved complex, [Os 3 (CO) 10 (l-C 8 H 6 S)], is also obtained [2,5]. Arce et al have reported that [Os 3 (CO) 10 (MeCN) 2 ] reacts with dibenzothiophene in refluxing cyclohexane to affords only one product, the nonacarbonyl species [Os 3 (CO) 9 (l 3 -C 12 H 6 S)(l-H) 2 ] [3]. Recently, we have demonstrated that the unsaturated triosmium cluster [(l-H)Os 3 (CO) 8 {l 3 -g 2 -Ph 2 PCH 2 P(Ph)C 6 H 4 }] reacts with benzothiophene at 139°C to give three triosmium compounds, [Os 3 (CO) 7 (l-PPh 2 )(l-PMePh)(l 3 -g 2 -C 6 H 4 )], [Os 3 (CO) 8 (l-CO)(l 3 -g 2 -PPh(C 6 H 4 )CH 2 PPh)] and [Os 3 (CO) 7 (l 3 -g 2 -PPh(C 6 H 4 )CH 2 PPh) (l 3 -g 3 -C 8 H 5 S)(l-H)] [7]; the first two of which are derived from the activation of P-C and C-H bonds of the diphosphine ligand and do not contain any benzothiophene-derived ligand; whereas, the last compound contains an unusual l 3 -g 2 -benzothienyl ligand (Scheme 1).…”

“…Recently, we have demonstrated that the unsaturated triosmium cluster [(l-H)Os 3 (CO) 8 {l 3 -g 2 -Ph 2 PCH 2 P(Ph)C 6 H 4 }] reacts with benzothiophene at 139°C to give three triosmium compounds, [Os 3 (CO) 7 (l-PPh 2 )(l-PMePh)(l 3 -g 2 -C 6 H 4 )], [Os 3 (CO) 8 (l-CO)(l 3 -g 2 -PPh(C 6 H 4 )CH 2 PPh)] and [Os 3 (CO) 7 (l 3 -g 2 -PPh(C 6 H 4 )CH 2 PPh) (l 3 -g 3 -C 8 H 5 S)(l-H)] [7]; the first two of which are derived from the activation of P-C and C-H bonds of the diphosphine ligand and do not contain any benzothiophene-derived ligand; whereas, the last compound contains an unusual l 3 -g 2 -benzothienyl ligand (Scheme 1). It is well documented that in addition to their ability to maintain the metal cluster framework intact during chemical reactions the dppm ligand in [Ru 3 (CO) 10 -(l-dppm)] (1) can also undergo C-H and P-C bond cleavage and M-H and M-C bond forming reactions to give many interesting reactions [8][9][10][11]. Adams et al reported the thermal transformation of the coordinated PMe 2 Ph ligands in [Ru 6 (CO) 15 (PMe 2 Ph)(l 6 -C)] to give a series of interesting hexaruthenium carbide complexes [Ru 6 (CO) 13 -(PMe 2 )(l 3 -g 3 -Me 2 PC 6 H 4 )(l 6 -C)], [Ru 6 (CO) 14 (PMe 2 Ph)(lg 2 -MePhPCH 2 )(l 6 -C)(l-H)], [Ru 6 (CO) 14 (l-PMe 2 )(l-g 2 -MePhPCH 2 )(l 6 -C)], and [Ru 6 (CO) 12 (l-PMe 2 ) 2 (l 3 -g 2 -C 6 H 4 )-(l 6 -C)] via C-H and P-H bond cleavages [12].…”