Author: Sean Clapham
Publisher:
ISBN: 9780494397831
Category :
Languages : en
Pages : 404
Book Description
The new air-sensitive ruthenium and osmium amido-hydrido complexes RuH(NHCMe 2CMe2NH2)(PPh3)2 and OsH(NHCMe 2CMe2NH2)(PPh3)2 have been synthesized and characterized. The hydrogenation of ketones to alcohols using these catalysts was explored. This included exploring the reactivity of these complexes toward hydrogen gas, ketones and alcohols, as well as performing kinetic experiments. The behaviour of the ruthenium and osmium systems were compared and mechanisms were proposed. Density functional calculations were carried out to model the proposed mechanisms and these were compared with experimental results. RuH(NHCMe2CMe2NH2)(PPh 3)2 was reacted with formic acid to generate RuH(OCHO)(NH 2CMe2CMe2NH2)(PPh3) 2, a model compound for the transfer of hydrogen from ruthenium to a ketone. The reactivity of the amido complexes towards weakly acidic compounds, HX, to generate new diamino complexes of the type MHX(NH2CMe 2CMe2NH2)(PPh3)2 (M = Ru or Os, X = H, OPh, NCCHCN, CH(COOMe)2, CCPh, OPPh2, OP(OEt)2, p-SC6H4OMe) was explored. Useful correlations were drawn relating the effect that the ligand trans to hydride has on the NMR and infrared spectra of these compounds. The complex RuH(OPh)(NH 2CMe2CMe2NH2)(PPh3) 2 hydrogen bonds with an equivalent of phenol to generate RuH(OPh···HOPh)(NH 2CMe2CMe2NH2)(PPh3) 2, which contains an interesting 6-membered ring as a result. This structure is similar to the proposed transition state for the alcohol-assisted splitting of dihydrogen by OsH(NHCMe2CMe2NH2)(PPh 3)2. The novel ruthenium complexes RuHX(1,2-NH2C 6H10NH2)(PPh3)2 (X = OPh, NCCHCN, CCPh, OPPh2, OP(OEt)2, p-SC6H 4OMe) were generated from the reaction of RuHCl(1,2-NH2C 6H10NH2)(PPh3)2 with HX and base. The complexes RuH(CCPh)(diamine)(PPh3)2 (diamine = NH2CMe2CMe2NH2 or 1,2-NH 2C6H10NH2) catalyze the hydrogenation of acetophenone to 1-phenylethanol, but less efficiently than the amido complexes. The complexes MH(CH(COOMe)2)(NH2CMe2CMe 2NH2)(PPh3)2 (M = Ru or Os) and the amido complexes also catalyze the Michael addition of dimethylmalonate to 2-cyclohexen-1-one. The reaction of RuH(NCCHCN)(NH2CMe2CMe 2NH2)(PPh3)2 with 2-cyclohexen-1-one leads to the formation of the trapped Michael adduct RuH(NCC(C6H 9O)CN)(NH2CMe2CMe2NH2)(PPh 3)2. The structure of this complex was used in proposing a mechanism for Michael addition reactions catalyzed by the amido complexes. The relative reactivity and strength of the osmium and ruthenium amido bonds were investigated through a series of competition experiments where HX (X = Cl, OPh, NCCHCN, p-SC6H4OMe) was transferred from OsHX(NH2CMe2CMe2NH2)(PPh 3)2 to RuH(NHCMe2CMe2NH2)(PPh 3)2 leading to RuHX(NH2CMe2CMe 2NH2)(PPh3)2 and OsH(NHCMe2CMe 2NH2)(PPh3)2.
Amido-hydrido Complexes of Ruthenium and Osmium
Author: Sean Clapham
Publisher:
ISBN: 9780494397831
Category :
Languages : en
Pages : 404
Book Description
The new air-sensitive ruthenium and osmium amido-hydrido complexes RuH(NHCMe 2CMe2NH2)(PPh3)2 and OsH(NHCMe 2CMe2NH2)(PPh3)2 have been synthesized and characterized. The hydrogenation of ketones to alcohols using these catalysts was explored. This included exploring the reactivity of these complexes toward hydrogen gas, ketones and alcohols, as well as performing kinetic experiments. The behaviour of the ruthenium and osmium systems were compared and mechanisms were proposed. Density functional calculations were carried out to model the proposed mechanisms and these were compared with experimental results. RuH(NHCMe2CMe2NH2)(PPh 3)2 was reacted with formic acid to generate RuH(OCHO)(NH 2CMe2CMe2NH2)(PPh3) 2, a model compound for the transfer of hydrogen from ruthenium to a ketone. The reactivity of the amido complexes towards weakly acidic compounds, HX, to generate new diamino complexes of the type MHX(NH2CMe 2CMe2NH2)(PPh3)2 (M = Ru or Os, X = H, OPh, NCCHCN, CH(COOMe)2, CCPh, OPPh2, OP(OEt)2, p-SC6H4OMe) was explored. Useful correlations were drawn relating the effect that the ligand trans to hydride has on the NMR and infrared spectra of these compounds. The complex RuH(OPh)(NH 2CMe2CMe2NH2)(PPh3) 2 hydrogen bonds with an equivalent of phenol to generate RuH(OPh···HOPh)(NH 2CMe2CMe2NH2)(PPh3) 2, which contains an interesting 6-membered ring as a result. This structure is similar to the proposed transition state for the alcohol-assisted splitting of dihydrogen by OsH(NHCMe2CMe2NH2)(PPh 3)2. The novel ruthenium complexes RuHX(1,2-NH2C 6H10NH2)(PPh3)2 (X = OPh, NCCHCN, CCPh, OPPh2, OP(OEt)2, p-SC6H 4OMe) were generated from the reaction of RuHCl(1,2-NH2C 6H10NH2)(PPh3)2 with HX and base. The complexes RuH(CCPh)(diamine)(PPh3)2 (diamine = NH2CMe2CMe2NH2 or 1,2-NH 2C6H10NH2) catalyze the hydrogenation of acetophenone to 1-phenylethanol, but less efficiently than the amido complexes. The complexes MH(CH(COOMe)2)(NH2CMe2CMe 2NH2)(PPh3)2 (M = Ru or Os) and the amido complexes also catalyze the Michael addition of dimethylmalonate to 2-cyclohexen-1-one. The reaction of RuH(NCCHCN)(NH2CMe2CMe 2NH2)(PPh3)2 with 2-cyclohexen-1-one leads to the formation of the trapped Michael adduct RuH(NCC(C6H 9O)CN)(NH2CMe2CMe2NH2)(PPh 3)2. The structure of this complex was used in proposing a mechanism for Michael addition reactions catalyzed by the amido complexes. The relative reactivity and strength of the osmium and ruthenium amido bonds were investigated through a series of competition experiments where HX (X = Cl, OPh, NCCHCN, p-SC6H4OMe) was transferred from OsHX(NH2CMe2CMe2NH2)(PPh 3)2 to RuH(NHCMe2CMe2NH2)(PPh 3)2 leading to RuHX(NH2CMe2CMe 2NH2)(PPh3)2 and OsH(NHCMe2CMe 2NH2)(PPh3)2.
Publisher:
ISBN: 9780494397831
Category :
Languages : en
Pages : 404
Book Description
The new air-sensitive ruthenium and osmium amido-hydrido complexes RuH(NHCMe 2CMe2NH2)(PPh3)2 and OsH(NHCMe 2CMe2NH2)(PPh3)2 have been synthesized and characterized. The hydrogenation of ketones to alcohols using these catalysts was explored. This included exploring the reactivity of these complexes toward hydrogen gas, ketones and alcohols, as well as performing kinetic experiments. The behaviour of the ruthenium and osmium systems were compared and mechanisms were proposed. Density functional calculations were carried out to model the proposed mechanisms and these were compared with experimental results. RuH(NHCMe2CMe2NH2)(PPh 3)2 was reacted with formic acid to generate RuH(OCHO)(NH 2CMe2CMe2NH2)(PPh3) 2, a model compound for the transfer of hydrogen from ruthenium to a ketone. The reactivity of the amido complexes towards weakly acidic compounds, HX, to generate new diamino complexes of the type MHX(NH2CMe 2CMe2NH2)(PPh3)2 (M = Ru or Os, X = H, OPh, NCCHCN, CH(COOMe)2, CCPh, OPPh2, OP(OEt)2, p-SC6H4OMe) was explored. Useful correlations were drawn relating the effect that the ligand trans to hydride has on the NMR and infrared spectra of these compounds. The complex RuH(OPh)(NH 2CMe2CMe2NH2)(PPh3) 2 hydrogen bonds with an equivalent of phenol to generate RuH(OPh···HOPh)(NH 2CMe2CMe2NH2)(PPh3) 2, which contains an interesting 6-membered ring as a result. This structure is similar to the proposed transition state for the alcohol-assisted splitting of dihydrogen by OsH(NHCMe2CMe2NH2)(PPh 3)2. The novel ruthenium complexes RuHX(1,2-NH2C 6H10NH2)(PPh3)2 (X = OPh, NCCHCN, CCPh, OPPh2, OP(OEt)2, p-SC6H 4OMe) were generated from the reaction of RuHCl(1,2-NH2C 6H10NH2)(PPh3)2 with HX and base. The complexes RuH(CCPh)(diamine)(PPh3)2 (diamine = NH2CMe2CMe2NH2 or 1,2-NH 2C6H10NH2) catalyze the hydrogenation of acetophenone to 1-phenylethanol, but less efficiently than the amido complexes. The complexes MH(CH(COOMe)2)(NH2CMe2CMe 2NH2)(PPh3)2 (M = Ru or Os) and the amido complexes also catalyze the Michael addition of dimethylmalonate to 2-cyclohexen-1-one. The reaction of RuH(NCCHCN)(NH2CMe2CMe 2NH2)(PPh3)2 with 2-cyclohexen-1-one leads to the formation of the trapped Michael adduct RuH(NCC(C6H 9O)CN)(NH2CMe2CMe2NH2)(PPh 3)2. The structure of this complex was used in proposing a mechanism for Michael addition reactions catalyzed by the amido complexes. The relative reactivity and strength of the osmium and ruthenium amido bonds were investigated through a series of competition experiments where HX (X = Cl, OPh, NCCHCN, p-SC6H4OMe) was transferred from OsHX(NH2CMe2CMe2NH2)(PPh 3)2 to RuH(NHCMe2CMe2NH2)(PPh 3)2 leading to RuHX(NH2CMe2CMe 2NH2)(PPh3)2 and OsH(NHCMe2CMe 2NH2)(PPh3)2.
The Chemistry of Ruthenium, Rhodium, Palladium, Osmium, Iridium and Platinum
Author: Stanley E. Livingstone
Publisher: Elsevier
ISBN: 1483158403
Category : Science
Languages : en
Pages : 225
Book Description
The Chemistry of Ruthenium, Rhodium, Palladium, Osmium, Iridium and Platinum
Publisher: Elsevier
ISBN: 1483158403
Category : Science
Languages : en
Pages : 225
Book Description
The Chemistry of Ruthenium, Rhodium, Palladium, Osmium, Iridium and Platinum
Chemistry of Ruthenium and Osmium Polypyridyl Complexes
Author: Xiaohong Chen
Publisher:
ISBN:
Category : Bipyridine
Languages : en
Pages : 516
Book Description
Publisher:
ISBN:
Category : Bipyridine
Languages : en
Pages : 516
Book Description
Structural Studies of Complexes of Ruthenium and Osmium with Fullerenes, Dinitrogen and Dihydrogen
Author: Fei Chen
Publisher:
ISBN:
Category : Fullerenes
Languages : en
Pages : 271
Book Description
Publisher:
ISBN:
Category : Fullerenes
Languages : en
Pages : 271
Book Description
Synthesis and Reactivities of Ruthenium and Osmium Amine Complexes
Author: 鄺士山
Publisher: Open Dissertation Press
ISBN: 9781374759879
Category :
Languages : en
Pages :
Book Description
This dissertation, "Synthesis and Reactivities of Ruthenium and Osmium Amine Complexes" by 鄺士山, Si-san, Kenneth, Kwong, was obtained from The University of Hong Kong (Pokfulam, Hong Kong) and is being sold pursuant to Creative Commons: Attribution 3.0 Hong Kong License. The content of this dissertation has not been altered in any way. We have altered the formatting in order to facilitate the ease of printing and reading of the dissertation. All rights not granted by the above license are retained by the author. DOI: 10.5353/th_b3123031 Subjects: Ruthenium Osmium
Publisher: Open Dissertation Press
ISBN: 9781374759879
Category :
Languages : en
Pages :
Book Description
This dissertation, "Synthesis and Reactivities of Ruthenium and Osmium Amine Complexes" by 鄺士山, Si-san, Kenneth, Kwong, was obtained from The University of Hong Kong (Pokfulam, Hong Kong) and is being sold pursuant to Creative Commons: Attribution 3.0 Hong Kong License. The content of this dissertation has not been altered in any way. We have altered the formatting in order to facilitate the ease of printing and reading of the dissertation. All rights not granted by the above license are retained by the author. DOI: 10.5353/th_b3123031 Subjects: Ruthenium Osmium
Comprehensive Coordination Chemistry II: Transition metal groups 7 and 8
Author: Jon A. McCleverty
Publisher: Pergamon
ISBN:
Category : Coordination compounds
Languages : en
Pages : 906
Book Description
Publisher: Pergamon
ISBN:
Category : Coordination compounds
Languages : en
Pages : 906
Book Description
Synthesis, Reactivities and Electrochemistry of Ruthenium and Osmium Oxo Complexes with Polypyridine Ligands
Author: 梁偉豪
Publisher:
ISBN: 9781374774773
Category :
Languages : en
Pages :
Book Description
Publisher:
ISBN: 9781374774773
Category :
Languages : en
Pages :
Book Description
Synthesis and Properties of Some Amine and Thioether Complexes of Ruthenium and Osmium
Author: Chi-Ming Che
Publisher: Open Dissertation Press
ISBN: 9781374762152
Category :
Languages : en
Pages :
Book Description
This dissertation, "Synthesis and Properties of Some Amine and Thioether Complexes of Ruthenium and Osmium" by Chi-ming, Che, 支志明, was obtained from The University of Hong Kong (Pokfulam, Hong Kong) and is being sold pursuant to Creative Commons: Attribution 3.0 Hong Kong License. The content of this dissertation has not been altered in any way. We have altered the formatting in order to facilitate the ease of printing and reading of the dissertation. All rights not granted by the above license are retained by the author. DOI: 10.5353/th_b3122986 Subjects: Ruthenium Osmium Complex compounds
Publisher: Open Dissertation Press
ISBN: 9781374762152
Category :
Languages : en
Pages :
Book Description
This dissertation, "Synthesis and Properties of Some Amine and Thioether Complexes of Ruthenium and Osmium" by Chi-ming, Che, 支志明, was obtained from The University of Hong Kong (Pokfulam, Hong Kong) and is being sold pursuant to Creative Commons: Attribution 3.0 Hong Kong License. The content of this dissertation has not been altered in any way. We have altered the formatting in order to facilitate the ease of printing and reading of the dissertation. All rights not granted by the above license are retained by the author. DOI: 10.5353/th_b3122986 Subjects: Ruthenium Osmium Complex compounds
Complexes of Ruthenium, Rhodium and Osmium with Some Dithioacid Ligands
Author: D. J. Cole-Hamilton
Publisher:
ISBN:
Category : Complex compounds
Languages : en
Pages : 0
Book Description
Publisher:
ISBN:
Category : Complex compounds
Languages : en
Pages : 0
Book Description
1, 1-dithiolate Complexes of Ruthenium and Osmium
Author: A. Ewan D. McQueen
Publisher:
ISBN:
Category : Osmium
Languages : en
Pages : 0
Book Description
Publisher:
ISBN:
Category : Osmium
Languages : en
Pages : 0
Book Description