The synthesis, X-ray structure, and substitution lability of chloro(2,3,7,8,12,13,17,18-octaethylporphinato)(triphenylphosphine)rhodium(III)

Thackray, David C.; Ariel, S.; Leung, T. W.; Menon, K. R.; James, Brian R.; Trotter, James

doi:10.1139/v86-404

Cited by 15 publications

(20 citation statements)

References 21 publications

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“…Another contributing factor may be the chelating effect of the pendant imino donors, drawing the metal center closer toward the carbazolide donor. There are no examples of structurally characterized carbazolide Rh complexes; one Rh III complex bearing a imino-pyrrolide ligand has been reported recently by Brunner et al and has a Rh−N(pyrrolide) bond length of 2.068 Å, which is considerably longer than the Rh−N(carbazolide) bond in 4 and closer to the values of 2.01−2.03 Å typically obtained for Rh III porphyrin complexes. − With the exception of the two phenyl substituents, the carbazolide ligand is planar to within ca. 0.07 Å, the rhodium atom lying within this plane.…”

Section: Resultsmentioning

confidence: 68%

Bis(imino)carbazolide Complexes of Rhodium: Highly Nucleophilic Ligands Exerting a Dramatic Accelerating Effect on MeI Oxidative Addition

et al. 2004

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Rhodium(I) complexes bearing a bis(imino)carbazolide ligand L and an additional neutral donor [LRh(C 2 H 4 ), 2; LRh(CO), 3] have been prepared via a salt metathesis reaction between NaL and the dimeric rhodium precursors [RhCl(C 2 H 4 ) 2 ] 2 and [RhCl(CO) 2 ] 2 , respectively. Complex 3 was also prepared by reaction of the free ligand with [RhCl(CO) 2 ] 2 , whereas a related reaction with [RhCl(C 2 H 4 ) 2 ] 2 afforded the dinuclear Rh I -Rh III ethyl complex 4. The X-ray crystal structure of 4 showed octahedral [bis(imino)carbazolide]Rh III (Cl)Et linked to square-planar bis(ethylene)Rh I Cl via chloride bridges. Kinetic studies on the oxidative addition of MeI to 3 to form the LRh III I(CO)Me complex 5 revealed a second-order rate constant of 1.66 M -1 s -1 in CH 2 Cl 2 at 25 °C, which corresponds to a reaction rate approximately 50 000 times faster than that observed for [RhI 2 (CO) 2 ] -.

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Section: Resultsmentioning

confidence: 68%

Bis(imino)carbazolide Complexes of Rhodium: Highly Nucleophilic Ligands Exerting a Dramatic Accelerating Effect on MeI Oxidative Addition

et al. 2004

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“…grade CO, N2, and Ar were obtained from Canada Liquid Air Ltd. All manipulations, including preparation of the complexes, were carried out under Ar using Schlenk techniques. General procedures used for recording optical, infrared, nmr, and mass spectra have been given elsewhere (16,17) (31P nmr shifts are relative to 85% H3PO4, downfield being positive). Gas chromatography (thermal conductivity) was performed on a Hewlett-Packard 5830A instrument using 6 ft. x 0.125 in.…”

Section: Methodsmentioning

confidence: 99%

Catalytic decarbonylation of aldehydes using iron(II) porphyrin complexes, and the crystal structure of (5,10,15,20-tetraphenylporphinato)bis(tri-n-butylphosphine)iron(II)

Belani¹,

James²,

Dolphin³

et al. 1988

Can. J. Chem.

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The complex (5,10,15,20-tetraphenylporphinato)bis(tri-n-butylphosphine)iron(II), 1, has been isolated in a triclinic crysgl form, a = 12.499(3), b = 12.528(2), c = 12.039(2) A, u = 116.39(1), P = 109.79(1), y = 98.13(1)", Z = 1, spacegroup P1.The structure was solved by conventional heavy atom methods and was refined by full-matrix least-squares procedures to R = 0.060 and R,, = 0.070 for 3551 reflections with I ? 3 u(l). The molecule, which has crystallographic 1-Ci symmetry, displays a relatively undistorted pseudo-octahedral coordination geometry with Fe-P = 2.346(1) and Fe-N = 1.998(3) and 1.993(3) A.In CH2C1, solution, 1 reacts with CO and aldehydes to generate the carbonyl(phosphine) derivative, and decarbonylation of phenylacetaldehyde to toluene becomes catalytic under an Ar stream. The aldehyde decarbonylations involve radical pathways via carbonyl loss from PhCH2C0. The hydrogen abstraction/initiation reaction probably utilizes trace O2 (and possibly trace (water); speculative mechanisms are discussed. [Traduit par la revue] Introduction Carbonylation reactions provide key steps in a range of homogeneously catalyzed processes of industrial importance (1, 2). Decarbonylation (for example, of aldehydes: RCHO +

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“…This arises because of the substantial displacement of the Rh atom from the porphyrin plane towards the phenyl ligand. In contrast, Rh±porphyrin adducts with axial ligands bound through an sp 3 donor atom, such as [Rh(OEP)Cl(PPh 3 )] (Thackray et al, 1986) and [Rh(por)(NMe 2 H) 2 ] + [por is TPP (Fleisher et al, 1973) or etioporphyrin I (Hanson et al, 1973)], manifest signi®cantly more planar cores, as do organometallic derivatives with compact alkyls, such as [Rh(OEP)(CH 3 )] (Whang & Kim, 1991).…”

Section: Commentmentioning

confidence: 99%

Superimposed saddle and ruffled distortions of the porphyrin in iodo(pyridine-N)(5,10,15,20-tetraphenylporphyrinato-κ⁴N)rhodium(III) toluene solvate

2001

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In the title compound, [RhI(C(44)H(28)N(4))(C(5)H(5)N)].C(7)H(8), the porphyrin ring experiences significant distortion from planarity (a saddle conformation with a superimposed ruffling), as a result of steric interactions with the 2,6-H atoms of the axial pyridine ligand. This also leads to a slight lengthening of the Rh-pyridine bond [Rh-N 2.102 (7) A] relative to those seen in other pyridine adducts of six-coordinate Rh(III). The metric parameters of the porphyrin core are comparable with those of related metalloporphyrin derivatives. No significant intermolecular interactions are observed between the metalloporphyrin and disordered solvate species.

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The synthesis, X-ray structure, and substitution lability of chloro(2,3,7,8,12,13,17,18-octaethylporphinato)(triphenylphosphine)rhodium(III)

Cited by 15 publications

References 21 publications

Bis(imino)carbazolide Complexes of Rhodium: Highly Nucleophilic Ligands Exerting a Dramatic Accelerating Effect on MeI Oxidative Addition

Bis(imino)carbazolide Complexes of Rhodium: Highly Nucleophilic Ligands Exerting a Dramatic Accelerating Effect on MeI Oxidative Addition

Catalytic decarbonylation of aldehydes using iron(II) porphyrin complexes, and the crystal structure of (5,10,15,20-tetraphenylporphinato)bis(tri-n-butylphosphine)iron(II)

Superimposed saddle and ruffled distortions of the porphyrin in iodo(pyridine-N)(5,10,15,20-tetraphenylporphyrinato-κ⁴N)rhodium(III) toluene solvate

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The synthesis, X-ray structure, and substitution lability of chloro(2,3,7,8,12,13,17,18-octaethylporphinato)(triphenylphosphine)rhodium(III)

Cited by 15 publications

References 21 publications

Bis(imino)carbazolide Complexes of Rhodium: Highly Nucleophilic Ligands Exerting a Dramatic Accelerating Effect on MeI Oxidative Addition

Bis(imino)carbazolide Complexes of Rhodium: Highly Nucleophilic Ligands Exerting a Dramatic Accelerating Effect on MeI Oxidative Addition

Catalytic decarbonylation of aldehydes using iron(II) porphyrin complexes, and the crystal structure of (5,10,15,20-tetraphenylporphinato)bis(tri-n-butylphosphine)iron(II)

Superimposed saddle and ruffled distortions of the porphyrin in iodo(pyridine-N)(5,10,15,20-tetraphenylporphyrinato-κ4N)rhodium(III) toluene solvate

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Superimposed saddle and ruffled distortions of the porphyrin in iodo(pyridine-N)(5,10,15,20-tetraphenylporphyrinato-κ⁴N)rhodium(III) toluene solvate