Theoretical study of the structures of electron-deficient d6 ML5 complexes. Importance of a .pi.-donating ligand

Riehl, Jean Frederic; Jean, Yves; Eisenstein, Odile; Pélissier, Maud

doi:10.1021/om00038a035

Cited by 219 publications

(204 citation statements)

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“…119,120 The structure is actually quite similar in nature to other rhodium-bisboryl compounds structurally characterized although the geometry in this case is best described as Y-shaped. .…”

mentioning

confidence: 75%

Transition Metal−Boryl Compounds: Synthesis, Reactivity, and Structure

et al. 1998

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mentioning

confidence: 75%

Transition Metal−Boryl Compounds: Synthesis, Reactivity, and Structure

et al. 1998

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“…Even considering that the trigonal bipyramid is a possible structure for five-coordinated metallic centers, theoretical studies have shown that this paramagnetic electronic state attributes instability to the complex due to the Jahn-Teller distortion [36]. The variations of enthalpy and Gibbs energy between these two isomers are predicted to be 2.5 and 2.0 kcal/mol, respectively, which indicates that the square pyramid is indeed a little more stable thermodynamically than the trigonal bipyramid structure (Fig.…”

Section: Theoretical Characterization Of the Initiator Complexmentioning

confidence: 99%

Structural and kinetic insights into the mechanism for ring opening metathesis polymerization of norbornene with [RuCl2(PPh3)2(piperidine)] as initiator complex

Fernandes

Silva

Neto

et al. 2015

Journal of Molecular Catalysis A: Chemical

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“…A view along the P-M-P axis reveals a rather strong deviation from an ideal trigonal arrangement (i.e., L-M-L angles of 1208) of the ligands in the equatorial plane towards a so called ™Y/ T∫-shaped structure. [23,24] The nitrogen atom in 6-Rh deviates by 14.88, and the chloride atom in 7-Ir by 19.88, from the bisection of the Ct1-M-Ct2 angle (M = Rh, Ir; Ct1/2 = centroids of the C=C trop bonds). In the 18-electron complexes 6-Rh and 7-Ir this distortion certainly has exclusively steric reasons [25] and is only detected in the solid state.…”

Section: Trans=cis-½irðtroppmentioning

confidence: 99%

Thermodynamic and Kinetic Data for Adduct Formation, cis–trans Isomerization and Redox Reactions of ML₄ Complexes: A Case study with Rhodium– and Iridium–tropp Complexes in d⁸, d⁹ and d¹⁰ Valence Electron Configurations (tropp= Dibenzotropylidene Phosphanes)

Breher

Rüegger

Mlakar

et al. 2004

Chemistry A European J

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The formation of adducts of the square-planar 16-electron complexes trans-[M(tropp(ph))(2)](+) and cis-[M(tropp(ph))(2)](+) (M=Rh, Ir; tropp(Ph)=5-diphenylphosphanyldibenzo[a,d]cycloheptene) with acetonitrile (acn) and Cl(-), and the redox chemistry of these complexes was investigated by various physical methods (NMR and UV-visible spectroscopy, square-wave voltammetry), in order to obtain some fundamental thermodynamic and kinetic data for these systems. A trans/cis isomerization cannot be detected for [M(tropp(ph))(2)](+) in non-coordinating solvents. However, both isomers are connected through equilibria of the type trans-[M(tropp(ph))(2)](+)+L<==>[ML(tropp(ph))(2)](n)<==>cis-[M(tropp(ph))(2)](+)+L, involving five-coordinate intermediates [ML(tropp(ph))(2)](n) (L=acn, n=+1; L=Cl(-), n=0). Values for K(d) (K(f)), that is, the dissociation (formation) equilibrium constant, and k(d) (k(f)), that is, the dissociation (formation) rate constant, were obtained. The formation reactions are fast, especially with the trans isomers (k(f)>1x10(5) m(-1) s(-1)). The reaction with the sterically more hindered cis isomers is at least one order of magnitude slower. The stability of the five-coordinate complexes [ML(tropp(ph))(2)](n) increases with Ir>Rh and Cl(-)>acn. The dissociation reaction has a pronounced influence on the square-wave (SW) voltammograms of trans/cis-[Ir(tropp(ph))(2)](+). With the help of the thermodynamic and kinetic data independently determined by other physical means, these reactions could be simulated and allowed the setting up of a reaction sequence. Examination of the data obtained showed that the trans/cis isomerization is a process with a low activation barrier for the four-coordinate 17-electron complexes [M(tropp(ph))(2)](0) and especially that a disproportionation reaction 2 trans/cis-[M(tropp(ph))(2)](0)-->[M(tropp(ph))(2)](+)+[M(tropp(ph))(2)](-) may be sufficiently fast to mask the true reactivity of the paramagnetic species, which are probably less reactive than their diamagnetic equilibrium partners.

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Theoretical study of the structures of electron-deficient d6 ML5 complexes. Importance of a .pi.-donating ligand

Cited by 219 publications

References 2 publications

Transition Metal−Boryl Compounds: Synthesis, Reactivity, and Structure

Transition Metal−Boryl Compounds: Synthesis, Reactivity, and Structure

Structural and kinetic insights into the mechanism for ring opening metathesis polymerization of norbornene with [RuCl2(PPh3)2(piperidine)] as initiator complex

Thermodynamic and Kinetic Data for Adduct Formation, cis–trans Isomerization and Redox Reactions of ML₄ Complexes: A Case study with Rhodium– and Iridium–tropp Complexes in d⁸, d⁹ and d¹⁰ Valence Electron Configurations (tropp= Dibenzotropylidene Phosphanes)

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Theoretical study of the structures of electron-deficient d6 ML5 complexes. Importance of a .pi.-donating ligand

Cited by 219 publications

References 2 publications

Transition Metal−Boryl Compounds: Synthesis, Reactivity, and Structure

Transition Metal−Boryl Compounds: Synthesis, Reactivity, and Structure

Structural and kinetic insights into the mechanism for ring opening metathesis polymerization of norbornene with [RuCl2(PPh3)2(piperidine)] as initiator complex

Thermodynamic and Kinetic Data for Adduct Formation, cis–trans Isomerization and Redox Reactions of ML4 Complexes: A Case study with Rhodium– and Iridium–tropp Complexes in d8, d9 and d10 Valence Electron Configurations (tropp= Dibenzotropylidene Phosphanes)

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Thermodynamic and Kinetic Data for Adduct Formation, cis–trans Isomerization and Redox Reactions of ML₄ Complexes: A Case study with Rhodium– and Iridium–tropp Complexes in d⁸, d⁹ and d¹⁰ Valence Electron Configurations (tropp= Dibenzotropylidene Phosphanes)