Mechanistic aspects of catalytic hydrogenation of ketones by rhodium(I)-peralkyldiphosphine complexes

Tani, Kazuhide; Tanigawa, Eiji; Tatsuno, Yoshitaka; Otsuka, Sei

doi:10.1016/0022-328x(85)87008-x

Cited by 58 publications

(17 citation statements)

References 33 publications

Supporting

Mentioning

Contrasting

Unclassified

Order By: Relevance

“…were as reported previously. Literature preparations were used to generate the bidentate ligands, P~~~P C H~C H~C H~P P~'~, dippp (17) and Pr'2PCH2CH2PPr'2, dippe (8).…”

Section: Generalmentioning

confidence: 99%

Coordinatively unsaturated binuclear clusters of rhodium. The reactivity of [{Prⁱ₂P(CH₂)_nPPrⁱ₂}Rh]₂(μ-H)₂ (n = 2, 3, and 4) with dihydrogen, and their use in the catalytic hydrogenation of olefins

Fryzuk¹,

Piers²,

Einstein³

et al. 1989

Can. J. Chem.

View full text Add to dashboard Cite

The coordinatively unsaturated binuclear rhodium hydrides [{Pri2P(CH2)nPPri2}Rh]2(μ-H)2 (n = 2: 1b; n = 3: 1c; n = 4: 1d) react rapidly with dihydrogen to yield the fluxional binuclear tetrahydrides [{Pri2P(CH2)nPPri2}RhH]((μ-H)3[Rh{Pri2P(CH2)nPPri2}] 2b–d(n = 2–4). The dihydride 1b was structurally characterized by single crystal X-ray diffraction. While the tetrahydrides 2b and 2c were found to be stable only in solution in the presence of excess dihydrogen, 2d was stable in the solid state. Three separate exchange processes were characterized for 2b–d via 1H and 31P{1H} NMR spectroscopy: intermolecular exchange with free dihydrogen, and two intramolecular processes exchanging the four hydride ligands. The geometry about the rhodium centres in the limiting structures involved in these processes is affected by the chelate ring size of the ancillary diphosphine ligand. A "rocking" process observed at low temperatures for each of these tetrahydrides has a ΔG≠ of <7.0(5) kcal/mol, 8.6(5) kcal/mol, and 11.5(5) kcal/mol for 2b, 2c, and 2d, respectively. The dihydrides 1b and 1c were found to catalyze the hydrogenation of 1-hexene. Turnover numbers of 850–950 h−1 and 700 h−1 were observed for 1b and 1c, respectively, along with isomerization side reactions. Catalyst concentration studies on the hydrogenation of styrene using 1c as the catalyst precursor revealed a decrease in turnover frequency with increasing total metal concentration, suggesting that the active catalyst is a mononuclear species. Chemical evidence suggests that a pathway involving binuclear intermediates is also available, but that in the 1c system at least, a pathway utilizing mononuclear species as intermediates predominates. Keywords: binuclear rhodium hydrides, homogeneous catalysis.

show abstract

“…were as reported previously. Literature preparations were used to generate the bidentate ligands, P~~~P C H~C H~C H~P P~'~, dippp (17) and Pr'2PCH2CH2PPr'2, dippe (8).…”

Section: Generalmentioning

confidence: 99%

Coordinatively unsaturated binuclear clusters of rhodium. The reactivity of [{Prⁱ₂P(CH₂)_nPPrⁱ₂}Rh]₂(μ-H)₂ (n = 2, 3, and 4) with dihydrogen, and their use in the catalytic hydrogenation of olefins

Fryzuk¹,

Piers²,

Einstein³

et al. 1989

Can. J. Chem.

View full text Add to dashboard Cite

show abstract

“…6.17), the hydrogenation of CO to MeOH, hydrogen transfer reactions and alcohol homologation. However, the successful isolation of such complexes from the catalytic systems was very rare [32][33][34][35][36][37]. [38].…”

Section: Complexes Resulting From Activation Of Alcohols: Hydrido(alkmentioning

confidence: 99%

“…Complex 50 was isolated in good yield as air-stable yellow crystals from the reaction of [Ir(cod){ i Pr 2 P(CH 2 ) 3 P i Pr 2 } ]ClO 4 (49) and PhC(O)C(O)NHCH 2 Ph under an atmospheric pressure of dihydrogen (Eq. 6.19) [33]. Although the crystallographic structure of complex 50 was not available, the complex was well characterized by elemental analysis as well as spectroscopic studies.…”

Section: Complexes Resulting From Activation Of Alcohols: Hydrido(alkmentioning

confidence: 99%

O–H Activation and Addition to Unsaturated Systems

Tani

Kataoka

2001

Catalytic Heterofunctionalization

Self Cite

View full text Add to dashboard Cite

“…Vor etwa zehn Jahren isolierten und charakterisierten wir einen Hydrido(alkoxo)-Iridiumkomplex als Modellverbindung für Intermediate rhodiumkatalysierter Hydrierungen von Carbonylverbindungen. [3] Milstein und Mitarbeiter berichteten über oxidative Additionen von Wasserstoff-Heteroatom-Gruppen an Rhodium-und Iridiumverbindungen unter Bildung unter anderem von Hydrido(alkoxo)-und Hydrido(hydroxo)-Komplexen. [4] Auch über die Isolierung einiger Hydrido(alkoxo)- [5] und Hydrido(hydroxo)-Komplexe [1d, 5d] von späten Übergangsmetallen ist berichtet worden.…”

Section: Kazuhide Tani* Aika Iseki Und Tsuneaki Yamagataunclassified

Leichte oxidative Addition von Methanol und Wasser an Peraryldiphosphan-IrI-Komplexe

1998

Self Cite

View full text Add to dashboard Cite

Mechanistic aspects of catalytic hydrogenation of ketones by rhodium(I)-peralkyldiphosphine complexes

Cited by 58 publications

References 33 publications

Coordinatively unsaturated binuclear clusters of rhodium. The reactivity of [{Prⁱ₂P(CH₂)_nPPrⁱ₂}Rh]₂(μ-H)₂ (n = 2, 3, and 4) with dihydrogen, and their use in the catalytic hydrogenation of olefins

Coordinatively unsaturated binuclear clusters of rhodium. The reactivity of [{Prⁱ₂P(CH₂)_nPPrⁱ₂}Rh]₂(μ-H)₂ (n = 2, 3, and 4) with dihydrogen, and their use in the catalytic hydrogenation of olefins

O–H Activation and Addition to Unsaturated Systems

Leichte oxidative Addition von Methanol und Wasser an Peraryldiphosphan-IrI-Komplexe

Contact Info

Product

Resources

About

Mechanistic aspects of catalytic hydrogenation of ketones by rhodium(I)-peralkyldiphosphine complexes

Cited by 58 publications

References 33 publications

Coordinatively unsaturated binuclear clusters of rhodium. The reactivity of [{Pri2P(CH2)nPPri2}Rh]2(μ-H)2 (n = 2, 3, and 4) with dihydrogen, and their use in the catalytic hydrogenation of olefins

Coordinatively unsaturated binuclear clusters of rhodium. The reactivity of [{Pri2P(CH2)nPPri2}Rh]2(μ-H)2 (n = 2, 3, and 4) with dihydrogen, and their use in the catalytic hydrogenation of olefins

O–H Activation and Addition to Unsaturated Systems

Leichte oxidative Addition von Methanol und Wasser an Peraryldiphosphan-IrI-Komplexe

Contact Info

Product

Resources

About

Coordinatively unsaturated binuclear clusters of rhodium. The reactivity of [{Prⁱ₂P(CH₂)_nPPrⁱ₂}Rh]₂(μ-H)₂ (n = 2, 3, and 4) with dihydrogen, and their use in the catalytic hydrogenation of olefins

Coordinatively unsaturated binuclear clusters of rhodium. The reactivity of [{Prⁱ₂P(CH₂)_nPPrⁱ₂}Rh]₂(μ-H)₂ (n = 2, 3, and 4) with dihydrogen, and their use in the catalytic hydrogenation of olefins