Reactions of ether-phosphine ruthenium hydride complexes with carbon disulfide and phenylacetylene: crystal structures of Ru(CO) Cl(P ∼ O)3(η2-S2CH and Ru(CO) Cl(P ∼ O)2(η2-S2CH)

Lindner, Ekkehard; Lin, Ying‐Chih; Geprägs, Michael; Yih, Kuang-Hway; Fawzi, Riad; Steimann, Manfred

doi:10.1016/0022-328x(95)05950-t

Cited by 12 publications

(2 citation statements)

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“…Complex 9a is octahedrally coordinated about the ruthenium with the C 6 Me 6 ligand occupying three coordination sites. The distorted octahedral geometry is due to a small S(1)−Ru(1)−S(2) angle of 71.41(2)°, similar to those in the corresponding ruthenium and osmium dithioformato complexes. , Both almost equal Ru−S bonds are comparable with reported values 4 ORTEP plot of 9a . 5 Selected Interatomic Distances (Å) and Angles (deg) for 9 a Bond Lengths Ru(1)−P(1) 2.3476(9) S(1)−C(1) 1.675(3) Ru(1)−S(1) 2.3814(9) S(2)−C(1) 1.672(3) Ru(1)−S(2) 2.3649(7) Bond Angles P(1)−Ru(1)−S(1) 91.31(2) S(2)−C(1)−S(1) 111.71(14) P(1)−Ru(1)−S(2) 89.46(3) C(1)−S(1)−Ru(1) 88.06(9) S(2)−Ru(1)−S(1) 71.41(2) C(1)−S(2)−Ru(1) 88.68(10)

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Section: Resultssupporting

confidence: 68%

Behavior of (Ether−phosphine)ruthenium(II) Complexes [(η⁶-C₆Me₆)RuH(P⌒O)][BF₄] Containing Reactive Ru−O and Ru−H Bonds toward Various Small Molecules and Their Application in Ring-Opening Metathesis Polymerization

et al. 1998

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The ruthenium(II) complexes [(η6-C6Me6)RuH(P⌒O)][BF4] (5a − c; P⌒O = η2-(O,P)-chelated ether−phosphine; a, Ph2PCH2CH2OCH3; b, Ph2PCH2C4H7O2 (C4H7O2 = 1,3-dioxanyl); c, Ph2PCH2C3H5O2 (C3H5O2 = 1,3-dioxolanyl)), each having a Ru−O and Ru−H functionality, were obtained by hydride abstraction from (η6-C6Me6)RuH2(P∼O) (4a − c, P∼O = η1-(P)-coordinated ligand) with Ph3CBF4. A facile Ru−O bond cleavage occurs when 5a − c are reacted with a variety of small molecules. Carbon monoxide, acetonitrile, tert-butyl isocyanide, and ethene were readily added to 5a − c, leading to the corresponding adducts [(η6-C6Me6)RuH(P∼O)L][BF4] (6a − c, 7a − c, 8a − c, 10a − c; L = CO, CH3CN, t-BuNC, C2H4). π/σ rearrangements with incorporation of the Ru−H bonds in 10a − c were not observed. If 5a − c were treated with carbon disulfide, both functionalities were required. Rupture of the Ru−O contact resulted in a π-CS2-coordinated intermediate followed by an insertion of CS2 into the Ru−H bond to give the dithioformato complexes [(η6-C6Me6)RuH(P∼O)(S2CH)][BF4] (9a − c). All compounds were obtained in excellent yields under mild conditions. The structures of 5a, 7c, 8c, and 9a were determined by single-crystal X-ray diffraction methods. Ring-opening metathesis polymerization of norbornene was achieved using complexes 5a − c as the catalyst precursors.

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…”

Section: Resultssupporting

confidence: 68%

Behavior of (Ether−phosphine)ruthenium(II) Complexes [(η⁶-C₆Me₆)RuH(P⌒O)][BF₄] Containing Reactive Ru−O and Ru−H Bonds toward Various Small Molecules and Their Application in Ring-Opening Metathesis Polymerization

et al. 1998

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“…Generally, the FT-IR absorption of the η 1 -dithioformato ligand appeared at 980−1012 cm −1 , whereas the η 2 -dithioformato ligand appeared at 900−960 cm −1 . 23,53 The above results suggested that both the η 1 -OC(H)O and η 1 -SC(H)S ligands in [Ru(η 1 -XC(H) X)(bpy) 2 (L)] + (X = O and S, L = PTA and PPh 3 ) complexes can bind to the Ru atom in an η 1 -fashion through the O and S atom, respectively. The summary of 1 H NMR, 31 P NMR, and FT-IR data for the complexes 1a−3b is displayed in Table 1.…”

Section: ■ Introductionmentioning

confidence: 86%

Kinetic Aspects for the Reduction of CO₂and CS₂with Mixed-Ligand Ruthenium(II) Hydride Complexes Containing Phosphine and Bipyridine

et al. 2014

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A new water-soluble ruthenium hydride complex [Ru(H)(bpy)2(PTA)]PF6 (bpy = 2,2'-bipyridine, PTA = 1,3,5-triaza-7-phosphaadamantane) (1a) was prepared. 1a reacted with CO2 and CS2 to give the corresponding formate and dithioformate complexes, respectively. Both the insertions of CO2 and CS2 into the Ru-H bond of 1a followed second-order kinetics. The second-order rate constant (k2) of CO2 insertion reaction varied from (9.40 ± 0.41) × 10(-4) M(-1) s(-1) in acetone to (1.13 ± 0.08) × 10(-1) M(-1) s(-1) in methanol; moreover, the ln(k2) is in good linear relationship with the acceptor number (AN) of the solvent used. Although, the k2 of CS2 insertion reaction ranged from (3.43 ± 0.10) M(-1) s(-1) in methanol to (24.0 ± 0.5) M(-1) s(-1) in N,N-dimethylformamide, which is 1000 times faster than CO2 insertion. Generally, the k2 of CS2 insertion increased with the static dielectric constant (D(s)) of the reaction medium investigated. For comparison purposes, we further investigated the reactivity of [Ru(H)(bpy)2(PPh3)]PF6 (PPh3 = triphenylphosphine) (1b) with CO2 and CS2. 1b reacted with CO2 slowly in the methanol with a k2 of (1.46 ± 0.09) × 10(-3) M(-1) s(-1), yielding a formate complex [Ru(η(1)-OC(H)═O)(bpy)2(PPh3)]PF6 (2b). The reaction of 1b with CS2 is 1000 times faster than that of CO2. The structures of 1a, 1b, and 2b were determined by X-ray crystallographic analysis.

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The Transition Metal Coordination Chemistry of Hemilabile Ligands

Slone

Weinberger

Mirkin

1999

Progress in Inorganic Chemistry

437

255

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Reactions of ether-phosphine ruthenium hydride complexes with carbon disulfide and phenylacetylene: crystal structures of Ru(CO) Cl(P ∼ O)3(η2-S2CH and Ru(CO) Cl(P ∼ O)2(η2-S2CH)

Cited by 12 publications

References 34 publications

Behavior of (Ether−phosphine)ruthenium(II) Complexes [(η⁶-C₆Me₆)RuH(P⌒O)][BF₄] Containing Reactive Ru−O and Ru−H Bonds toward Various Small Molecules and Their Application in Ring-Opening Metathesis Polymerization

Behavior of (Ether−phosphine)ruthenium(II) Complexes [(η⁶-C₆Me₆)RuH(P⌒O)][BF₄] Containing Reactive Ru−O and Ru−H Bonds toward Various Small Molecules and Their Application in Ring-Opening Metathesis Polymerization

Kinetic Aspects for the Reduction of CO₂and CS₂with Mixed-Ligand Ruthenium(II) Hydride Complexes Containing Phosphine and Bipyridine

The Transition Metal Coordination Chemistry of Hemilabile Ligands

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Reactions of ether-phosphine ruthenium hydride complexes with carbon disulfide and phenylacetylene: crystal structures of Ru(CO) Cl(P ∼ O)3(η2-S2CH and Ru(CO) Cl(P ∼ O)2(η2-S2CH)

Cited by 12 publications

References 34 publications

Behavior of (Ether−phosphine)ruthenium(II) Complexes [(η6-C6Me6)RuH(P⌒O)][BF4] Containing Reactive Ru−O and Ru−H Bonds toward Various Small Molecules and Their Application in Ring-Opening Metathesis Polymerization

Behavior of (Ether−phosphine)ruthenium(II) Complexes [(η6-C6Me6)RuH(P⌒O)][BF4] Containing Reactive Ru−O and Ru−H Bonds toward Various Small Molecules and Their Application in Ring-Opening Metathesis Polymerization

Kinetic Aspects for the Reduction of CO2and CS2with Mixed-Ligand Ruthenium(II) Hydride Complexes Containing Phosphine and Bipyridine

The Transition Metal Coordination Chemistry of Hemilabile Ligands

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Behavior of (Ether−phosphine)ruthenium(II) Complexes [(η⁶-C₆Me₆)RuH(P⌒O)][BF₄] Containing Reactive Ru−O and Ru−H Bonds toward Various Small Molecules and Their Application in Ring-Opening Metathesis Polymerization

Behavior of (Ether−phosphine)ruthenium(II) Complexes [(η⁶-C₆Me₆)RuH(P⌒O)][BF₄] Containing Reactive Ru−O and Ru−H Bonds toward Various Small Molecules and Their Application in Ring-Opening Metathesis Polymerization

Kinetic Aspects for the Reduction of CO₂and CS₂with Mixed-Ligand Ruthenium(II) Hydride Complexes Containing Phosphine and Bipyridine