Unusual structural and chemical trends within a series of binuclear rhodium carbonyl halide complexes and the structure of one member of this series, trans-[Rh2Cl2(CO)2((C6H5)2PCH2P(C6H5)2)2]

Cowie, Martin; Dwight, Stephen K.

doi:10.1021/ic50211a004

Cited by 74 publications

(31 citation statements)

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“…group has an average Rh-C distance of 1.974(9) A and the Rh-C(C0)-Rh angle is 85.6(4)", as e~pected. '~ The observed Rh-C distance is comparable with the values of 1.960(8) and I .974(7) A reported for [Rh2Brz(p-CO)(p-dppm)2]and [Rh2Cl,(p-CO)(pdema)(dppm)2] l 6 (dema = dimethyl acetylenedicarboxylate) respectively, and is significantly shorter than the values observed in other rhodium complexes containing bridging carbonyl ligands. The geometrical features of (1) (Figures1 and 2) suggest the possibility of a comparison with those of 'A-frame ' complexes 3.17 having dppm ligands.…”

supporting

confidence: 77%

Synthesis and some reactions of binuclear η-cyclopentadienyl rhodium complexes containing bis(diphenylphosphino)methane and small molecules (CO, SO₂, or SnCl₂) as bridging ligands. Crystal and molecular structure of [Rh₂(η-C₅H₅)₂(µ-CO)(µ-Ph₂PCH₂PPh₂)]

Faraone¹,

Brunò²,

Schiavo³

et al. 1984

J. Chem. Soc., Dalton Trans.

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supporting

confidence: 77%

Synthesis and some reactions of binuclear η-cyclopentadienyl rhodium complexes containing bis(diphenylphosphino)methane and small molecules (CO, SO₂, or SnCl₂) as bridging ligands. Crystal and molecular structure of [Rh₂(η-C₅H₅)₂(µ-CO)(µ-Ph₂PCH₂PPh₂)]

Faraone¹,

Brunò²,

Schiavo³

et al. 1984

J. Chem. Soc., Dalton Trans.

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“…The two Rh-P bonds in 9 (mean 2.252(1) Å) are shorter than the values found in the binuclear rhodium complex [Rh 2 Cl 2 (CO) 2 (dppm) 2 ] (2.3141 (9), 2.3315 (9) Å). 21 …”

Section: Molecular Structures Of [Cp Tt 2 Zr(µ 3 -S) 2 {Rh(co) 2 } 2 mentioning

confidence: 99%

Synthesis, Reactivity, and Catalytic Activity of Triangular ZrM₂(M = Rh, Ir) Early−Late Heterobimetallic Complexes

et al. 2003

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SummaryReactions of the zirconium-sulfide metallocene anion [Cp tt 2 ZrS 2 ] 2-(Cp tt = η 5 -1,3-di-tertbutylcyclopentadienyl) with [{M(µ-Cl) with one molar-equiv of bis(diphenylphosphino)methane (dppm) gave the cisoid complexes [Cp tt 2 Zr(µ 3 -S) 2 {M(CO)} 2 (µ-dppm)] (M = Rh (9), Ir) with evolution of carbon monoxide.Monodentate phosphites, P(OMe) 3 and P(OPh) 3, react with 6 to give mixtures of the transoid and cisoid isomers [Cp tt 2 Zr(µ 3 -S) 2 {Rh(CO)(P(OR) 3 )} 2 ], which also exhibit a restricted rotation of the Cp tt rings. The molecular structures of complexes 6 and 9 have been determined by X-ray diffraction methods. Compound 6 in the presence of P-donor ligands, P(OMe) 3 , P(OPh) 3, and 40 PPh 3 , is a precursor of catalyst for the hydroformylation of oct-1-ene under mild conditions of pressure and temperature.

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“…The behaviour described above has precedent in the literature with the activation of small molecules such as CO,8c SO 2 11 and CS 2 10 mediated by 4 , in which the ligand first coordinates to one rhodium centre, then evolves to form a bridging ligand that is symmetrically coordinated to both metals. Although this study suggests that the activation of P 4 promoted by the dinuclear complex 4 may proceed through a cooperative effect of the two vicinal rhodium sites, we cannot rule out the possibility that 5 is a byproduct of the reaction.…”

Section: Resultsmentioning

confidence: 93%

“…Building on these examples of stepwise activation of P 4 by two different transition‐metal moieties (Scheme ), we investigated the direct activation of P 4 by a homobimetallic complex, namely the dimeric Rh I carbonyl complex8 trans ‐[RhCl(CO)(dppm)] 2 ( 4 ), which is known to activate small molecules such as alkynes,9 CO,8c and CS 2 10…”

Section: Introductionmentioning

confidence: 99%

The Bimetallic Activation of White Phosphorus by trans‐[RhCl(CO)(dppm)]₂ Results in a Tetrahedro‐Rh₂P₂ Moiety

et al. 2014

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Keywords: Metal-metal interactions / Phosphorus / Rhodium / Phosphine ligandsThe reaction of trans-[RhCl(CO)(dppm)] 2 with P 4 carried out at room temperature showed that bimetallic cooperation resulted in the cleavage of P 4 , giving a μ,η 2 -P 2 (μ-κ 2 :κ 2 -P 2 ) ligand coordinated to the two metal centres. The new complex cis-[Rh 2 (CO) 2 (μ-dppm) 2 (μ,η 2 -P 2 )] has been fully characterised in solution by NMR spectroscopy and in the solid state by single-crystal X-ray diffraction. The Rh-Rh distance of 2.723(18) Å is consistent with the presence of a metal-metal[a] Consiglio

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Unusual structural and chemical trends within a series of binuclear rhodium carbonyl halide complexes and the structure of one member of this series, trans-[Rh2Cl2(CO)2((C6H5)2PCH2P(C6H5)2)2]

Cited by 74 publications

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Synthesis and some reactions of binuclear η-cyclopentadienyl rhodium complexes containing bis(diphenylphosphino)methane and small molecules (CO, SO₂, or SnCl₂) as bridging ligands. Crystal and molecular structure of [Rh₂(η-C₅H₅)₂(µ-CO)(µ-Ph₂PCH₂PPh₂)]

Synthesis and some reactions of binuclear η-cyclopentadienyl rhodium complexes containing bis(diphenylphosphino)methane and small molecules (CO, SO₂, or SnCl₂) as bridging ligands. Crystal and molecular structure of [Rh₂(η-C₅H₅)₂(µ-CO)(µ-Ph₂PCH₂PPh₂)]

Synthesis, Reactivity, and Catalytic Activity of Triangular ZrM₂(M = Rh, Ir) Early−Late Heterobimetallic Complexes

The Bimetallic Activation of White Phosphorus by trans‐[RhCl(CO)(dppm)]₂ Results in a Tetrahedro‐Rh₂P₂ Moiety

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Unusual structural and chemical trends within a series of binuclear rhodium carbonyl halide complexes and the structure of one member of this series, trans-[Rh2Cl2(CO)2((C6H5)2PCH2P(C6H5)2)2]

Cited by 74 publications

References 0 publications

Synthesis and some reactions of binuclear η-cyclopentadienyl rhodium complexes containing bis(diphenylphosphino)methane and small molecules (CO, SO2, or SnCl2) as bridging ligands. Crystal and molecular structure of [Rh2(η-C5H5)2(µ-CO)(µ-Ph2PCH2PPh2)]

Synthesis and some reactions of binuclear η-cyclopentadienyl rhodium complexes containing bis(diphenylphosphino)methane and small molecules (CO, SO2, or SnCl2) as bridging ligands. Crystal and molecular structure of [Rh2(η-C5H5)2(µ-CO)(µ-Ph2PCH2PPh2)]

Synthesis, Reactivity, and Catalytic Activity of Triangular ZrM2(M = Rh, Ir) Early−Late Heterobimetallic Complexes

The Bimetallic Activation of White Phosphorus by trans‐[RhCl(CO)(dppm)]2 Results in a Tetrahedro‐Rh2P2 Moiety

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Synthesis and some reactions of binuclear η-cyclopentadienyl rhodium complexes containing bis(diphenylphosphino)methane and small molecules (CO, SO₂, or SnCl₂) as bridging ligands. Crystal and molecular structure of [Rh₂(η-C₅H₅)₂(µ-CO)(µ-Ph₂PCH₂PPh₂)]

Synthesis and some reactions of binuclear η-cyclopentadienyl rhodium complexes containing bis(diphenylphosphino)methane and small molecules (CO, SO₂, or SnCl₂) as bridging ligands. Crystal and molecular structure of [Rh₂(η-C₅H₅)₂(µ-CO)(µ-Ph₂PCH₂PPh₂)]

Synthesis, Reactivity, and Catalytic Activity of Triangular ZrM₂(M = Rh, Ir) Early−Late Heterobimetallic Complexes

The Bimetallic Activation of White Phosphorus by trans‐[RhCl(CO)(dppm)]₂ Results in a Tetrahedro‐Rh₂P₂ Moiety