Complexes of Ruthenium, Osmium, Rhodium, and Iridium Containing Hydride Carbonyl, or Nitrosyl Ligands

Ahmad, Naseer; Levison, J. J.; Robinson, Stephen D.; Uttley, M. F.; Wonchoba, E. R.; Parshall, G. W.

doi:10.1002/9780470132463.ch13

Cited by 364 publications

(81 citation statements)

References 33 publications

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“…These criteria led us to the classic hydride complex RuHCl(CO)-A C H T U N G T R E N N U N G (PPh 3 ) 3 1, itself commercially available, and accessible in one step and quantitative yields from RuCl 3 . [36] Addition of excess PCy 3 to a stirred suspension of 1 in benzene or toluene effects quantitative conversion to 2 within 3 h at 40 8C. An aliquot removed at this Scheme 1.…”

Section: %mentioning

confidence: 99%

“…C 6 D 6 was degassed by consecutive freeze/pump/thaw cycles and dried over activated sieves (Linde 4 ). RuHCl(CO)A C H T U N G T R E N N U N G (PPh 3 ) 3 1 [36] and RuHCl(CO)A C H T U N G T R E N N U N G (NHC)A C H T U N G T R E N N U N G (PPh 3 ) 8 [26] were prepared according to literature methods. NMR spectra were recorded on a Bruker Avance 300 or AMX-500 spectrometer at 298 K, using the residual proton signals of the deuterated solvent as internal standard ( To a pale pink suspension of 1 (0.500 g, 0.525 mmol) in benzene (200 mL) was added solid PCy 3 (0.450 g, 1.61 mmol), causing an immediate color change to pale yellow.…”

Section: Experimental Section General Proceduresmentioning

confidence: 99%

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Improved Syntheses of Versatile Ruthenium Hydridocarbonyl Catalysts Containing Electron‐Rich Ancillary Ligands

et al. 2008

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Section: %mentioning

confidence: 99%

Section: Experimental Section General Proceduresmentioning

confidence: 99%

Improved Syntheses of Versatile Ruthenium Hydridocarbonyl Catalysts Containing Electron‐Rich Ancillary Ligands

et al. 2008

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“…GC/ MS analyses were carried out using Hewlett Packard gas chromatograph (GC 5890 Series II) and mass spectrometer (MS 5972 Series) equipped with mass selective detector (70 eV). [RuCl(H)(CO)(PPh 3 ) 3 ] was obtained by a published method [22]. The other chemicals were commercially available.…”

Section: Methodsmentioning

confidence: 99%

Ruthenium Catalyzed Reactions of Aldehydes: Molecular Structures of Ruthenium Complexes with Aldehyde Ligands

Sorkau

Wagner

Steinborn

et al. 2005

Transition Met Chem

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RuCl(H)(CO)(PPh 3 ) 3 ](2) was found to catalyze, in the presence of H 2 C=CHSiMe 3 (3), the trimerisation of aldehydes RCHO [R=Et (4a), i-Bu (4b)] yielding 1,3,5-trioxanes (5) and the aldol condensation yielding a,b-unsaturated aldehydes (6). When (4a) was used as a reactant, from these reaction mixtures, the ruthenium complex [RuCl 2 (CO)(PPh 3 ) 2 (EtCH@CMeACHO-jO)] (7) having the aldol condensation product as the ligand crystallized. In the analogous reaction with (4b), the complex [RuCl 2 (CO)(PPh 3 ) 2 (i-BuCHO-jO)] (8) with the aldehyde as ligand was obtained. The constitution of these complexes was established by single-crystal X-ray diffraction measurements. The ruthenium centers are octahedrally coordinated having the aldehyde and the carbonyl ligand in mutually trans positions (coordination index: OC-6-12). The aldehydes are monodentately coordinated via the carbonyl oxygen atom (jO). The coordination induced elongations of the C@O double bonds [1.242(4) Å (7), 1.234(4) Å (8)] indicate an activation of the aldehydes. Furthermore, the RuACO bond lengths [1.842(4) Å (7), 1.823(4) Å (8)] exhibit a relatively low trans influence of the aldehyde ligands. The formation of the complexes (7) and (8) give an indication that the Lewis acidity of the ruthenium center is of importance for aldehyde activation in the catalytic process.

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“…18 For a comparison of catalytic activity of such systems with Ru(0) complexes, the complexes bis(triphenylphosphine) tricarbonyl ruthenium(0), Ru(CO) 3 (PPh 3 ) 2 and trirutheniumdodecacarbonyl, Ru 3 (CO) 12 were prepared according to published procedures. 19 2.1 Catalytic hydroformylation reactions. The hydroformylation of 1-hexene was carried out in a 100-mL stainless steel high pressure autoclave (Chemical Press) equipped with a PID temperature controller, thermocouple, gas feed valve, sampling valve, and safety valve.…”

Section: Methodsmentioning

confidence: 99%

MECHANISTIC STUDY OF A RUTHENIUM HYDRIDE COMPLEX OF TYPE [RuH(CO)(N-N)(PR3)2]+ AS CATALYST PRECURSOR FOR THE HYDROFORMYLATION REACTION OF 1-HEXENE

Moya

Yáñez-S

Pérez

et al. 2016

J. Chil. Chem. Soc.

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The catalytic activity of systems of type [RuH(CO)(N-N)(PR 3 ) 2 ] + was evaluated in the hydroformylation reaction of 1-hexene. The observed activity is explained through a reaction mechanism on the basis of the quantum theory. The mechanism included total energy calculations for each of the intermediaries of the elemental steps considered in the catalytic cycle. The deactivation of the catalyst precursors takes place via dissociation of the polypyridine ligand and the subsequent formation of thermodynamically stable species, such as RuH(CO) 3 (PPh 3 ) 2 and RuH 3 (CO)(PPh 3 ) 2 , which interrupt the catalytic cycle. In addition, the theoretical study allows to explain the observed regioselectivity which is defined in two steps: (a) the hydride migration reaction with an anti-Markovnikov orientation to produce the alkyl-linear-complex (3.1a), which is more stable by 19.4 kJ/mol than the Markovnikov orientation (alkyl-branched-complex) (3.1b); (b) the carbon monoxide insertion step generates the carbonyl alkyl-linear specie (4.1a) which is more stable by 9.5 kJ/mol than the alternative species (4.1b), determining the preferred formation of heptanal in the hydroformylation of 1-hexene.

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Complexes of Ruthenium, Osmium, Rhodium, and Iridium Containing Hydride Carbonyl, or Nitrosyl Ligands

Cited by 364 publications

References 33 publications

Improved Syntheses of Versatile Ruthenium Hydridocarbonyl Catalysts Containing Electron‐Rich Ancillary Ligands

Improved Syntheses of Versatile Ruthenium Hydridocarbonyl Catalysts Containing Electron‐Rich Ancillary Ligands

Ruthenium Catalyzed Reactions of Aldehydes: Molecular Structures of Ruthenium Complexes with Aldehyde Ligands

MECHANISTIC STUDY OF A RUTHENIUM HYDRIDE COMPLEX OF TYPE [RuH(CO)(N-N)(PR3)2]+ AS CATALYST PRECURSOR FOR THE HYDROFORMYLATION REACTION OF 1-HEXENE

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