Rhodium complexes of 2-(diphenylphosphino)pyridine. X-ray crystal and molecular structure of bis[2-(diphenylphosphino)pyridine]-.mu.-carbonyl-dichlorodirhodium and some chemical transformations of this complex

Farr, James P.; Olmstead, Marilyn M.; Hunt, Catherine H.; Balch, Alan L.

doi:10.1021/ic50218a045

Cited by 74 publications

(32 citation statements)

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“…Such an arrangement is typical of these dimeric complexed ligands bridged by a bidentate heterodonor. The corresponding structure of Rh 2 (CO)Cl 2 (PPh 2 py) has been published and the geometry discussed in detail [23,24]. The spectroscopic data is consistent with the data supplied for the pyridylphosphane derivative published previously.…”

Section: 3supporting

confidence: 80%

Synthesis and structures of (3-methyl-2-pyridyl)diphenylphosphane derivatives of metal clusters

Jääskeläinen

Haukka

Riihimäki

et al. 2004

Journal of Organometallic Chemistry

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Section: 3supporting

confidence: 80%

Synthesis and structures of (3-methyl-2-pyridyl)diphenylphosphane derivatives of metal clusters

Jääskeläinen

Haukka

Riihimäki

et al. 2004

Journal of Organometallic Chemistry

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“…In another study, the formation of a -CO species was found when using a pyridinylphosphine ligand. 38 Our IR investigation excludes the formation of such species, although it could play a role as an intermediate as found for other ligand redistribution processes. 30 Independently on how complex 6 is generated, this remains the major species in solution, as shown by IR spectroscopy, when this is maintained overnight under a high CO pressure (20 atm).…”

Section: (C) Identification Of the Dicarbonyl Complex Cis-rh(co)2cl(l)mentioning

confidence: 62%

Rh(I) Coordination Chemistry of Chiral α-Aminophosphine(η⁶-arene)chromium Tricarbonyl Ligands

et al. 2003

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The diastereoselective addition of Ph(2)PH to the chiral ortho-substituted eta(6)-benzaldimine complexes (eta(6)-o-X-C(6)H(4)CH=NAr)Cr(CO)(3) (1, X = MeO, Ar = p-C(6)H(4)OMe; 2, X = Cl, Ar = Ph) leads to the formation of the corresponding chiral aminophosphines (alpha-P,N) Ph(2)P-CH(Ar(1))-NHAr(2) (3, Ar(1) = o-C(6)H(4)(OCH(3))[Cr(CO)(3)], Ar(2) = p-C(6)H(4)OCH(3); 4, Ar(1) = o-C(6)H(4)Cl[Cr(CO)(3)], Ar(2) = Ph) in equilibrium with the starting materials. The uncomplexed benzaldimine (o-ClC(6)H(4)CH=NPh), 2', analogously produces an equilibrium amount of the corresponding aminophosphine Ph(2)P-CH(Ar(1))-NHAr(2) (4', Ar(1) = o-C(6)H(4)Cl, Ar(2) = Ph). Depending on the equilibrium constant, the subsequent addition of (1)/(2) equiv of [RhCl(COD)](2) (COD = 1,5-cyclooctadiene) leads to either Ph(2)PH oxidative addition in the case of 3 or to the corresponding [RhCl(COD)(alpha-P,N)] complexes [RhCl(COD)(Ph(2)P-CH[o-C(6)H(4)Cl[Cr(CO)(3)]]-NHPh)] (5) and [RhCl(COD)(Ph(2)P-CH(o-C(6)H(4)Cl)-NHPh)] (5') in the cases of the aminophosphines 4 and 4'. The addition of the latter ligands, as racemic mixtures, to (1)/(4) equiv of [Rh(CO)(2)Cl](2) leads to the [RhCl(CO)(alpha-P,N)(2)] complexes [RhCO(Ph(2)P-CH[o-C(6)H(4)Cl[Cr(CO)(3)]]-NHPh)(2)Cl] (7) or [RhCO(Ph(2)P-CH(o-C(6)H(4)Cl)-NHPh)(2)Cl] (7') as mixtures of (R(C),S(C))/(S(C),R(C)) and (R(C),R(C))/(S(C),S(C)) diastereomers. The rhodium complexes 5 and 7' have been fully characterized by IR and (31)P NMR spectroscopies and X-ray crystallography. These compounds exhibit intramolecular Rh-Cl.H-N interactions in the solid state and in solution. The stability of the new rhodium complexes has been studied under different CO pressures. Under 1 atm of CO, 5 is converted to an unstable complex [RhCl(CO)(2)(alpha-P,N)], 6, which undergoes ligand redistribution leading to 7 plus an unidentified complex. This reaction is inhibited under higher CO or syngas pressure, as confirmed by the observation of the same catalytic activity in hydroformylation when styrene was added to a catalytic mixture that was either freshly prepared or left standing for 20 h under high CO pressure.

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“…Nevertheless, recrystallization of this solid in the presence of free 1 ,&naphthyridine renders pure complex (8) which exhibits two v(C0) bands in the 2 100-2 OOO cm-' region characteristic of cis-dicarbonylrhodium complexes. Similarly complexes ( 1 16), ( 17), (20), and ( 21)]. However, the related complex [Rh(cod)(2Menapy)][C10,] ( 12) is mononuclear.…”

Section: Resultsmentioning

confidence: 99%

“…Bubbling carbon monoxide through dichloromethane suspensions of the binuclear complexes (16) or (20)…”

Section: Resultsmentioning

confidence: 99%

Complexes of rhodium(I) with 1,8-naphthyridine and related ligands. Crystal structure of [Rh₂(µ-napy)₂(nbd)₂][ClO₄]₂·H₂O

Tiripicchio¹,

Camellini²,

Usón³

et al. 1984

J. Chem. Soc., Dalton Trans.

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Rhodium complexes of 2-(diphenylphosphino)pyridine. X-ray crystal and molecular structure of bis[2-(diphenylphosphino)pyridine]-.mu.-carbonyl-dichlorodirhodium and some chemical transformations of this complex

Cited by 74 publications

References 2 publications

Synthesis and structures of (3-methyl-2-pyridyl)diphenylphosphane derivatives of metal clusters

Synthesis and structures of (3-methyl-2-pyridyl)diphenylphosphane derivatives of metal clusters

Rh(I) Coordination Chemistry of Chiral α-Aminophosphine(η⁶-arene)chromium Tricarbonyl Ligands

Complexes of rhodium(I) with 1,8-naphthyridine and related ligands. Crystal structure of [Rh₂(µ-napy)₂(nbd)₂][ClO₄]₂·H₂O

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Rhodium complexes of 2-(diphenylphosphino)pyridine. X-ray crystal and molecular structure of bis[2-(diphenylphosphino)pyridine]-.mu.-carbonyl-dichlorodirhodium and some chemical transformations of this complex

Cited by 74 publications

References 2 publications

Synthesis and structures of (3-methyl-2-pyridyl)diphenylphosphane derivatives of metal clusters

Synthesis and structures of (3-methyl-2-pyridyl)diphenylphosphane derivatives of metal clusters

Rh(I) Coordination Chemistry of Chiral α-Aminophosphine(η6-arene)chromium Tricarbonyl Ligands

Complexes of rhodium(I) with 1,8-naphthyridine and related ligands. Crystal structure of [Rh2(µ-napy)2(nbd)2][ClO4]2·H2O

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Rh(I) Coordination Chemistry of Chiral α-Aminophosphine(η⁶-arene)chromium Tricarbonyl Ligands

Complexes of rhodium(I) with 1,8-naphthyridine and related ligands. Crystal structure of [Rh₂(µ-napy)₂(nbd)₂][ClO₄]₂·H₂O