| 1. |
- Begum, Noorjahan, et al.
(författare)
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Chelate and bridge diphosphine isomerization: triosmium and triruthenium clusters containing 1,1-bis(diphenylphosphino)ferrocene (dppf)
- 2007
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Ingår i: Organometallics. - : American Chemical Society (ACS). - 1520-6041 .- 0276-7333. ; 26:25, s. 6462-6472
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Tidskriftsartikel (refereegranskat)abstract
- The coordination mode of dppf {dppf = 1,1'-bis(diphenylphosphino)ferrocene} at triosmium and triruthenium carbonyl clusters has been studied. Heating [Os3(CO)12] with dppf in the presence of Me3NO in benzene at 60 C furnishes three triosmium compounds, [Os3(CO)11(1-dppf)] (1), [Os3(CO)10(2-dppf)] (2), and [Os3(CO)10(-dppf)] (3) in 10, 20, and 30% yields, respectively. Reaction of the labile cluster [Os3(CO)10(MeCN)2] with dppf at room temperature also gives 1, 2, and 3 (5, 10, and 35% yields). Treatment of 1, which contains a pendant diphosphine, with Me3NO at room temperature affords 2 via a ring closure reaction, whereas heating 2, in which the dppf ligand is chelating, at 110 C affords the thermodynamically stable bridging isomer 3, in which phosphorus atoms are bound at equatorial positions. Reaction of the unsaturated cluster [Os3(CO)10(-H)2] (4) with dppf in refluxing THF affords the bridging complex [Os3(CO)8(-dppf)(-H)2] (6) in high yield as the sole product. Hydrogenation of 3 with H2 at 110 C at 1 atm also yields 6. Reactions of both the saturated [Os3(CO)10(-dppm)] (7) and electron-deficient [Os3(CO)8{3-Ph2PCH2P(Ph)C6H4}(-H)] (8) with dppf at 110 C and at room temperature respectively yield [Os3(CO)9(-dppm)(1-dppf)] (9) and [Os3(CO)8(-dppm)(2-dppf)] (10). Compound 9 converts to 10 at 110 C via CO loss and phosphorus coordination. Reaction of [Ru3(CO)12] with dppf in the presence of Me3NO affords the dihydroxy-bridged complex, [Ru3(CO)8(-dppf)(-OH)2] (13), together with the previously reported compounds [Ru3(CO)10(-dppf)] (11) and [Ru3(CO)8(-dppf)2] (12).
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| 2. |
- Begum, Noorjahan, et al.
(författare)
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Reaction of [Ru-3(CO)(12)] with tri(2-furyl)phosphine: Di- and tri-substituted triruthenium and phosphido-bridged diruthenium complexes
- 2008
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Ingår i: Journal of Organometallic Chemistry. - : Elsevier BV. - 0022-328X. ; 693:8-9, s. 1645-1655
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Tidskriftsartikel (refereegranskat)abstract
- Reaction of [Ru-3(CO)(12)] with tri(2-furyl)phosphine, P(C4H3O)(3), at 40 degrees C in the presence of a catalytic amount of Na[Ph2CO] furnishes two triruthenium complexes [Ru-3(CO)(10){P(C4H3O)(3)}(2)] (1) and [Ru-3(CO)(9){P(C4H3O)(3)}(3)] (2) with the ligand coordinated through the phosphorus atom. Treatment of 1 and 2 with Me3NO at 40 degrees C affords the dinuclear phosphido-bridged complexes [Ru-2(CO)(6)(mu-eta(1),eta(2)-C4H3O){mu-P(C4H3O)(2)}] (3) and [Ru-2(CO)(5)(mu-eta(1),eta(2)-C4H3O){mu-P(C4H3O)(2)}{P(C4H3O)(3)}] (4), respectively, that are formed via phosphorus-carbon bond cleavage of a coordinated phosphine followed by coordination of the dissociated furyl moiety to the diruthenium center in a sigma,pi-alkenyl mode. Reaction of [Ru-3(CO)(12)] with tri(2-furyl) phosphine in refluxing benzene gives, in addition to 3 and 4, low yields of the cyclometallated complex [Ru-3(CO)(9){mu-eta(1),eta(1)-P(C4H3O)(2)(C4H2O)}(2)] (5). Treatment of 3 with EPh3 (E = P, As, Sb) at room temperature yields the monosubstituted derivatives [Ru-2(CO)(5)(mu-eta(1),eta(2)-C4H3O){mu-P(C4H3O)(2)}(EPh3)] (E = P, 8; E = As, 9; E = Sb, 10). Similar reactions of 3 with P(C4H3O)(3), P(OMe)(3) and (BuNC)-N-t yield 4, [Ru-2(CO)(5)(mu-eta(1),eta(2)-C4H3O){mu-P(C4H3O)(2)}{P(OMe)(3)}] (11) and [Ru-2(CO)(5)(mu-eta(1),eta(2)-C4H3O){mu-P(C4H3O)(2)}(NCBut)] (12), respectively. The molecular structures of complexes 3, 4 and 8 have been elucidated by single crystal X-ray diffraction studies. Each complex contains a bridging sigma,pi-alkenyl group and while in 4 the phosphine is bound to the sigma-coordinated metal atom, in 8 it is at the pi-bound atom. Protonation of 3 and 4 gives the hydride complexes [(mu-H)Ru-2(CO)(6)(mu-eta(1),eta(2)-C4H3O){mu-P(C4H3O)(2)}](+) (6) and [(mu-H)Ru-2(CO)(5)(mu-eta(1),eta(2)-C4H3O){mu-P(C4H3O)(2)}{P(C4H3O)(3)}] (+) (7), respectively, while heating 3 with dimethylacetylenedicarboxylate (DMAD) in refluxing toluene gives the cyclotrimerization product, C-6(CO2Me)(6).
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| 3. |
- Ghosh, Shishir, et al.
(författare)
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Reactivity of phenyldi(2-thienyl) phosphine towards group 7 metal carbonyls: Carbon-phosphorus bond activation
- 2009
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Ingår i: Inorganica Chimica Acta. - : Elsevier BV. - 0020-1693. ; 362:15, s. 5175-5182
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Tidskriftsartikel (refereegranskat)abstract
- Addition of phenyldi(2-thienyl) phosphine (PPhTh2) to [Re-2(CO)(10-n)(NCMe)(n)] (n = 1, 2) affords the substitution products [Re-2(CO)(10-n)(PhPTh2)(n)] (1, 2) together with small amounts of fac-[ClRe(CO)(3)(PPhTh2)(2)] (3) (n = 2). Reaction of [Re-2(CO)(10)] with PPhTh2 in refluxing xylene affords a mixture which includes 2, [Re-2(CO)(7)(PPhTh2)(mu-PPhTh)(mu-H)] (4), [Re-2(CO)(7)(PPhTh2)(mu-PPhTh)(mu-eta(1), kappa(1)(S)-C4H3S)] (5) and mer[HRe(CO)(3)(PPhTh2)(2)] (6). Phosphido-bridged 4 and 5 are formed by the carbon-phosphorus bond cleavage of the coordinated PPhTh2 ligand, the cleaved thienyl group being retained in the latter. Reaction of [Mn-2(CO)(10)] with PPhTh2 in refluxing toluene affords [Mn-2(CO)(9)(PPhTh2)] (7) and the carbon-phosphorus bond cleavage products [Mn-2(CO)(6)(mu-PPhTh)(mu-eta(1),eta(5)-C4H3S)] (8) and [Mn-2(CO)(5)(PPhTh2)(mu-PPhTh)(mu-eta(1),eta(5)-C4H3S)] (9). Both 8 and 9 contain a bridging thienyl ligand which is bonded to one manganese atom in a eta(5)-fashion. (C) 2009 Elsevier B. V. All rights reserved.
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| 4. |
- Rahman, Mohammad A., et al.
(författare)
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Reaction of tri(2-furyl)phosphine with triosmium clusters: C-H and P-C activation to afford furyne and phosphinidene ligands
- 2011
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Ingår i: Journal of Organometallic Chemistry. - : Elsevier BV. - 0022-328X. ; 696:2, s. 607-612
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Tidskriftsartikel (refereegranskat)abstract
- Addition of tri(2-furyl)phosphine. PFu(3), to [Os-3(CO)(10)(mu-H)(2)] at room temperature gives [HOs3(CO)(10)(PFu(3)) (mu-H)] (1), while in refluxing toluene the same reactants afford [Os-3(CO)(9)(mu(3)-PFu(2)(C4H2O))(mu-H)] (2) resulting from orthometallatation of a furyl ring. Reaction of PFu(3) with [Os-3(CO)(10-n)(NCMe)n] (n = 0, 1, 2) affords the substituted clusters [Os-3(CO)(12-n)(PFu(3))(n)] (n = 1-3) (3-5), the phosphine ligands occupying equatorial position in all cases. Heating [Os-3(CO)(11)(PFu(3))] (3) in refluxing octane gives [Os-3(CO)(9)(mu(3)-PFu)(mu(3)-eta(2)-C4H2O)] (6) which results from both carbon-hydrogen and carbon-phosphorus bond activation and contains both mu(3)-eta(2)-furyne and furylphosphinidene ligands. All new clusters have been characterized by spectroscopic methods together with single crystal X-ray diffraction for 2,3 and 6. (c) 2010 Published by Elsevier B.V.
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| 5. |
- Uddin, Md Miaz, et al.
(författare)
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Thermal transformations of tris(2-thienyl)phosphine (PTh3) at low-valent ruthenium cluster centers : Part I. Carbon-hydrogen, carbon-phosphorus and carbon-sulfur bond activation yielding Ru3(CO)8L{μ-Th2P(C4H2S)}(μ-H) (L = CO, PTh3), Ru3(CO)7(μ-PTh2)2(μ3-η2-C4H2S), Ru4(CO)9(μ-CO)2(μ4-η2-C4H2S)(μ4-PTh) and Ru5(CO)11(μ-PTh2)(μ4-η4-C4H3)(μ4-S)
- 2016
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Ingår i: Journal of Organometallic Chemistry. - : Elsevier BV. - 0022-328X. ; 812, s. 197-206
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Tidskriftsartikel (refereegranskat)abstract
- Reaction of Ru3(CO)12 with tris(2-thienyl)phosphine (PTh3) in CH2Cl2 at room temperature or in THF in the presence of a catalytic amount of Na[Ph2CO] furnishes the carbonyl substitution products Ru3(CO)11(PTh3) (1), Ru3(CO)10(PTh3)2 (2), and Ru3(CO)9(PTh3)3 (3). Heating 1 in toluene affords the cyclometalated cluster Ru3(CO)9{μ-Th2P(C4H2S)}(μ-H) (4) resulting from carbonyl loss and carbon-hydrogen bond activation, and both 4 and the substituted derivative Ru3(CO)8{μ-Th2P(C4H2S)}(PTh3)(μ-H) (5) resulted from the direct reaction of Ru3(CO)12 and PTh3 at 110 °C in toluene. Interestingly, thermolysis of 2 in benzene at 80 °C affords 5 together with phosphido-bridged Ru3(CO)7(μ-PTh2)2(μ3-η2-C4H2S) (6) resulting from both phosphorus-carbon and carbon-hydrogen bond activation of coordinated PTh3 ligand(s). Cluster 6 is the only product of the thermolysis of 2 in toluene. Heating cyclometalated 4 with Ru3(CO)12 in toluene at 110 °C yielded the tetranuclear phosphinidine cluster, Ru4(CO)9(μ-CO)2(μ4-η2-C4H2S)(μ4-PTh) (7), resulting from carbon-phosphorus bond scission, together with the pentaruthenium sulfide cluster, Ru5(CO)11(μ-PTh2)(μ4-η4-C4H3)(μ4-S) (8), in which sulfur is extruded from a thiophene ring. All the new compounds were characterized by elemental analysis, mass spectrometry, IR and NMR spectroscopy, and by single crystal X-ray diffraction analysis in case of clusters 4, 6, 7, and 8. Cluster 4 consists of a triangular ruthenium framework containing a μ3-Th2P(C4H2S) ligand, while 6 consists of a ruthenium triangle containing η2-μ3-thiophyne ligand and two edge-bridging PTh2 ligands. Cluster 7 exhibits a distorted square arrangement of ruthenium atoms that are capped on one side by a μ4-phosphinidene ligand and on the other by a 4e donating μ4-η2-C4H2S ligand. The structure of 8 represents a rare example of a pentaruthenium wing-tip bridged-butterfly skeleton capped by μ4-S and μ4-η4-C4H3 ligands. The compounds 4, 6, 7, and 8 have been examined by density functional theory (DFT), and the lowest energy structure computed coincides with the X-ray diffraction structure. The hemilabile nature of the activated thienyl ligand in 4 and 6 has also been computationally investigated.
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| 6. |
- Uddin, Md. Nazim, et al.
(författare)
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Carbon-Phosphorus Bond Activation of Tri(2-thienyl)phosphine at Dirhenium and Dimanganese Centers
- 2009
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Ingår i: Organometallics. - : American Chemical Society (ACS). - 1520-6041 .- 0276-7333. ; 28:5, s. 1514-1523
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Tidskriftsartikel (refereegranskat)abstract
- Reaction of [Re-2(CO)(9)(NCMe)] with tri(2-thienyl)phosphine (PTh3) in refluxing cyclohexane affords three substituted dirhenium complexes: [Re-2(CO)(9)(PTh3)] (1), [Re-2(CO)(8)(NCMe)(PTh3)] (2), and [Re-2(CO)(8)(PTh3)(2)] (3). Complex 2 was also obtained from the room-temperature reaction of [Re-2(CO)(8)(NCMe)(2)] with PTh3 and is an unusual example in which the acetonitrile and phosphine ligands are coordinated to the same rhenium atom. Thermolysis of 1 and 3 in refluxing xylene affords [Re-2(CO)(8)(mu-PTh2)(mu-eta(1):kappa(1)-C4H3S)] (4) and [Re-2(CO)(7)(PTh3)(mu-PTh2)(mu-H)] (5), respectively, both resulting from carbon-phosphorus bond cleavage of a coordinated PTh3 ligand. Reaction of [Re-2(CO)10] and PTh3 in refluxing xylene gives a complex mixture of products. These products include 3-5, two further binuclear products, [Re-2(CO)(7)(PTh3)(mu-PTh2)(mu-eta(1):kappa(1)-C4H3S)] (6) and [Re-2(CO)(7)(mu-kappa(1):kappa(2)-Th2PC4H2SPTh)(mu-eta(1):kappa(1)-C4H3S )] (7), and the mononuclear hydrides [ReH(CO)(4)(PTh3)] (8) and trans-[ReH(CO)(3)(PTh3)(2)] (9). Binuclear 6 is structurally similar to 4 and can be obtained from reaction of the latter with 1 equiv of PTh3. Formation of 7 involves a series of rearrangements resulting in the formation of a unique new diphosphine ligand, Th2PC4H2SPTh. Reaction of [Mn-2(CO)(10)] with PTh3 in refluxing toluene affords the phosphine-substituted product [Mn-2(CO)(9)(PTh3)] (10) and two carbon-phosphorus bond cleavage products, [Mn-2)(CO)(6)(mu-PTh2)(mu-eta(1):eta(5)-C4H3S)] (11) and [Mn-2(CO)(5)(PTh3)(mu-PTh2)(mu-PTh2)(mu-eta(1):eta(5)-C4H3S)] (12). Both 11 and 12 contain a bridging thienyl ligand that is bonded to one manganese atom in a eta(5)-fashion. The molecular structures of eight of these new complexes were established by single-crystal X-ray diffraction studies, allowing a detailed analysis of the disposition of the coordinated ligands.
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| 7. |
- Uddin, Md. Nazim, et al.
(författare)
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Reactivity of triruthenium thiophyne and furyne clusters: competitive S-C and P-C bond cleavage reactions and the generation of highly unsymmetrical alkyne ligands
- 2008
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Ingår i: Dalton Transactions. - : Royal Society of Chemistry (RSC). - 1477-9234 .- 1477-9226. ; :44, s. 6219-6230
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Tidskriftsartikel (refereegranskat)abstract
- The synthesis and reactivity of the thiophyne and furyne clusters [Ru-3(CO)(7)(mu-dppm)(mu(3)-eta(2)-C4H2E){mu-P(C4H3E)(2)}(mu-H)] (E = S, O) is reported. Addition of P(C4H3E)(3) to [Ru-3(CO)(10)(mu-dppm)] (1) at room temperature in the presence of Me3NO gives simple substitution products [Ru-3(CO)(9)(mu-dppm)-P(C4H3E)(3)}] (E = S, 2; E = O, 3). Mild thermolysis in the presence of further Me3NO affords the thiophyne and furyne complexes [Ru-3(CO)(7)(mu-dppm)(mu(3)-eta(2)-C4H2E){mu-P(C4H3E)(2)}(mu-H)] (E = S, 4; E = O, 6) resulting from both carbon-hydrogen and carbon-phosphorus bond activation. In each the C4H2E (E = S, O) ligand donates 4-electrons to the cluster and the rings are tilted with respect to the m-dppm and the phosphido-bridged open triruthenium unit. Heating 4 at 80 degrees C leads to the formation of the ring-opened cluster [Ru-3(CO)(5)(mu-CO)(mu-dppm)(mu(3)-eta(3)-SC4H3){mu-P(C4H3S)(2)}] (5) resulting from carbon-sulfur bond scission and carbon- hydrogen bond formation and containing a ring-opened mu(3)-eta(3)-1-thia-1,3-butadiene ligand. In contrast, a similar thermolysis of 3 affords the phosphinidene cluster [Ru-3(CO)(7)(mu-dppm)(mu(3)-eta(2)-C4H2O){mu(3)-P(C4H3O)}] (7) resulting from a second phosphorus-carbon bond cleavage and (presumably) elimination of furan. Treatment of 4 and 6 with PPh3 affords the simple phosphine-substituted products [Ru-3(CO)(6)(PPh3)(mu-ppm)(mu(3)-eta(2)-C4H2E){mu-P(C4H3E)(2)}(mu-H)] (E = S, 8; E = O, 9). Both thiophyne and furyne clusters 4 and 6 readily react with hydrogen bromide to give [Ru-3(CO)(6)Br(mu-Br)(mu-dppm)(mu(3)-eta(2)-eta(1)-C4H2E){mu-P(C4H3E)(2) }(mu-H)] (E = S, 10; E = O, 11) containing both terminal and bridging bromides. Here the alkynes bind in a highly unsymmetrical manner with one carbon acting as a bridging alkylidene and the second as a terminally bonded Fisher carbene. As far as we are aware, this binding mode has only previously been noted in ynamine complexes or those with metals in different oxidation states. The crystal structures of seven of these new triruthenium clusters have been carried out, allowing a detailed analysis of the relative orientations of coordinated ligands.
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