Alkylation catalytique de substrats allyliques en présence de complexes nitrosyles

Roustan, J. L.; Bisnaire, Michel; Park, George; Guillaume, P.

doi:10.1016/0022-328x(88)83089-4

Cited by 8 publications

(7 citation statements)

References 3 publications

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“…The previously reported photoelectron spectra of the phosphine complexes CpMn(CO) 2 (PMe 3 ) and Co(CO) 2 NOPMe 3 along with the parent carbonyls CpMn-(CO) 3 and Co(CO) 3 NO are also included for comparison. The two parent compounds are widely used as catalysts in synthetic organic chemistry; 5,6 they have important use in chemical vapor deposition, 7,8 and Co(CO) 3 NO can be used as a precursor of cobalt nanotubes. 9,10 Both the parent compounds CpMn(CO) 3 11,12 and Co-(CO) 3 NO 13 and many transition-metal phosphine complexes [14][15][16][17][18][19][20][21] have been studied using photoelectron spectroscopy.…”

Section: Introductionmentioning

confidence: 99%

“…The previously reported photoelectron spectra of the phosphine complexes CpMn(CO) 2 (PMe 3 ) and Co(CO) 2 NOPMe 3 along with the parent carbonyls CpMn(CO) 3 and Co(CO) 3 NO are also included for comparison. The two parent compounds are widely used as catalysts in synthetic organic chemistry; , they have important use in chemical vapor deposition, , and Co(CO) 3 NO can be used as a precursor of cobalt nanotubes. , …”

Section: Introductionmentioning

confidence: 99%

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Photoelectron Spectra of Phosphine Analogue Complexes of Co(CO)₃NO and CpMn(CO)₃

et al. 2010

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The electronic structure of organometallic complexes with the phosphine analogue ligands trimethylarsine and trimethylstibine was studied. Four new complexes, CpMn(CO) 2 AsMe 3 , CpMn-(CO) 2 SbMe 3 , Co(CO) 2 NOAsMe 3 , and Co(CO) 2 NOSbMe 3 , were synthesized, and their He I and He II photoelectron spectra were recorded. The first ionization energies, which correspond to ionization from mainly metal d orbitals, are 6.83, 6.83, 7.58, and 7.69 eV, respectively. These numbers correspond to an approximately 1 eV uniform destabilization of the metal d orbitals, with respect to the parent carbonyls. The lone-pair orbital stabilization, with respect to the free ligands, was significant: 1.00, 0.94, 1.70, and 1.34 eV. The trends observed in these ionization energies were explained by the σand π-donor and π-acceptor properties of the ligands, on the basis of the changes in the hybridization of lone-pair orbitals.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Photoelectron Spectra of Phosphine Analogue Complexes of Co(CO)₃NO and CpMn(CO)₃

et al. 2010

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“…Transition-metal complexes are used as catalysts in numerous reactions of biological and industrial importance. Cobalt tricarbonyl nitrosyl has a particularly important role in organic chemistry, [1][2][3] chemical vapor deposition, [4][5][6] and even in nanotechnology. 7,8 Experiments show that phosphine substitution, due to its effect on the electronic structure and its steric demand, may strongly affect the stability and catalytic activity of transition-metal carbonyls.…”

Section: Introductionmentioning

confidence: 99%

Effect of Phosphine Substitution on the Electronic Structure of Cobalt Tricarbonyl Nitrosyl

2004

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The He-I ultraviolet photoelectron spectra of a series of phosphine-substituted organometallic complexes, Co(CO)2NOL (L = CO, PMe3, PEt3, PPr3, PBu3, PCy3, PPh3, and P(OMe)3) are reported. The first vertical ionization energy of the complexes was found to be 8.75 (CO), 7.85 (PMe3), 7.69 (PEt3), 7.47 (PPr3), 7.49 (PBu3), 7.71 (PCy3), 7.58 (PPh3), and 8.15 eV (P(OMe)3) ± 0.03 eV. Quantum chemical calculations at the HF, DFT (B3LYP), and EOMIP-CCSD levels of theory were employed to interpret both the trends in the series and the most important features of the spectra. Photoelectron spectra of some of the complexes are also reported at He-II photon energy. Intensity changes in the photoelectron bands between He-I and He-II photon energies are discussed on the basis of the orbital compositions.

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“…For example, Co(CO) 3 NO was used for producing phenylacetic acid and its derivatives by catalytic carbonylation 7 and for the catalytic alkylation of allylic substrates. 8 It is also widely used in constructing heterogeneous catalysts with chemical vapor deposition on zeolites. These catalysts were used for hydrodesulfurization 9,10 as well as for CO hydrogenation.…”

Section: Introductionmentioning

confidence: 99%

“…Cobalt tricarbonyl nitrosyl has numerous uses in both homogeneous and heterogeneous catalysis, chemical vapor deposition, and more recently in nanotechnology. For example, Co(CO) 3 NO was used for producing phenylacetic acid and its derivatives by catalytic carbonylation and for the catalytic alkylation of allylic substrates . It is also widely used in constructing heterogeneous catalysts with chemical vapor deposition on zeolites.…”

Section: Introductionmentioning

confidence: 99%

Consecutive and Parallel Dissociation of Energy-Selected Co(CO)₃NO⁺ Ions

Sztáray

Baer

2002

J. Phys. Chem. A

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Photoelectron photoion coincidence (PEPICO) spectroscopy has been used to investigate the dissociation dynamics of the cobalt tricarbonyl nitrosyl ion, Co(CO)3NO+. The ionization energy of Co(CO)3NO was measured from the threshold photoelectron spectrum to be 8.33 ± 0.04 eV. The dissociation of the molecular ion proceeds by two sequential carbonyl-loss steps and then a parallel carbonyl- or nitrosyl-loss step. The first two reactions were observed to be slow (lifetimes in the microsecond range). By simulating the resulting asymmetric time-of-flight peak shapes and the relative ion abundances (breakdown curves), 0 K onsets for the following fragment ions were determined: Co(CO)2NO+, 9.28 ± 0.02 eV; CoCONO+, 10.43 ± 0.02 eV; CoNO+, 12.00 ± 0.02 eV; CoCO+, 12.07 ± 0.02 eV. Combining these onsets with the experimental adiabatic ionization energy of Co(CO)3NO+, the three cobalt−carbonyl bond energies in Co(CO) x NO+ (x = 1−3) were determined along with the cobalt-nitrosyl bond energy in CoCONO+. Using a literature value for the [Co−CO]+ bond energy, the 0 K heats of formation of the above-mentioned molecular and fragment ions and of the neutral compound, Co(CO)3NO, were determined. Using these thermochemical data, the cobalt−nitrosyl bond energies were also derived for Co(CO)3NO+ and CoNO+. The latter is in good agreement with a theoretical literature value, while the first one explains why there is no observable NO loss from the molecular ion, Co(CO)3NO+. Room-temperature values of the heats of formation are also given using the calculated harmonic frequencies.

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Alkylation catalytique de substrats allyliques en présence de complexes nitrosyles

Cited by 8 publications

References 3 publications

Photoelectron Spectra of Phosphine Analogue Complexes of Co(CO)₃NO and CpMn(CO)₃

Photoelectron Spectra of Phosphine Analogue Complexes of Co(CO)₃NO and CpMn(CO)₃

Effect of Phosphine Substitution on the Electronic Structure of Cobalt Tricarbonyl Nitrosyl

Consecutive and Parallel Dissociation of Energy-Selected Co(CO)₃NO⁺ Ions

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Alkylation catalytique de substrats allyliques en présence de complexes nitrosyles

Cited by 8 publications

References 3 publications

Photoelectron Spectra of Phosphine Analogue Complexes of Co(CO)3NO and CpMn(CO)3

Photoelectron Spectra of Phosphine Analogue Complexes of Co(CO)3NO and CpMn(CO)3

Effect of Phosphine Substitution on the Electronic Structure of Cobalt Tricarbonyl Nitrosyl

Consecutive and Parallel Dissociation of Energy-Selected Co(CO)3NO+ Ions

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Photoelectron Spectra of Phosphine Analogue Complexes of Co(CO)₃NO and CpMn(CO)₃

Photoelectron Spectra of Phosphine Analogue Complexes of Co(CO)₃NO and CpMn(CO)₃

Consecutive and Parallel Dissociation of Energy-Selected Co(CO)₃NO⁺ Ions