Synthesis and Reactivity of Ruthenium Amine and Amido Complexes PDF Download
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Languages : en
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Author: David Michael Conner
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Category :
Languages : en
Pages : 393
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Keywords: Ruthenium amido, C-H bond activation, Ruthenium amine, Amdio.
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Languages : en
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Ru carbene complexes have been investigated for potential application toward carbon-nitrogen bond forming and breaking reactions. The reactivity of Grubbs-type olefin metathesis catalysts (Cl)2(L)(L')Ru=CHPh (L = L' = PCy3 or PPh3; L = PCy3 and L' = H2MesNHC) has been studied with cyclic and acyclic imines. The Ru benzylidene complex (Cl)2(PCy3)2Ru=CHPh undergoes a ligand exchange reaction with 1-pyrroline at room temperature, and oligomerizes 1-pyrroline at 90 oC. The low molecular weight poly(1-pyrroline) has been isolated and characterized. The Ru benzylidene complex has no reactivity toward acyclic imine C=N bonds, but reacts with enamine C=C bonds that form through tautomerization of imines. The Ru amido complexes, (PCP)Ru(CO)(NHPh) and (PCP)Ru(CO)(NHPh)(PMe3) (PCP = 2,6-(CH2P-t-Bu2)C6H3), have been synthesized and characterized. Reaction of (PCP)Ru(CO)(NHPh)(PMe3) with acetonitrile produces the amidinate complex (PCP)Ru(CO)(NHC(Me)NPh). Kinetic studies have demonstrated the formation of the amidinate complex occurs through dissociation of the PMe3 ligand, coordination of MeCN, and intramolecular nucleophilic attack of the amido ligand toward MeCN. The intramolecular nucleophilic attack reaction has been extensively studied with aromatic nitriles, carbodiimides, isocyanates, carboxamides and aldehydes. Reaction of (PCP)Ru(CO)(NHC(Me)NPh) with pentafluorobenzonitrile results in formation of a new amidinate complex (PCP)Ru(CO)(NHC(C6F5)NPh). The complex (PCP)Ru(CO)(NHC(C6F5)NPh) can initiate a C-F bond cleavage reaction of C6F5CN with ortho regioselectivity in the presence of ROH (R = H or Me). Reaction of five-coordinate complex (PCP)Ru(CO)(OTf) (OTf = OSO2CF3) with NaBAr'4 (Ar' = 3,5-(CF3)2C6H3) under different conditions results in formation of [(PCP)Ru(CO)(ClCH2Cl)][BAr'4], [(PCP)Ru(CO)(N2)][BAr'4] or [(PCP)Ru(CO)(FC6H5)][BAr'4]. Calculations have confirmed that the possible four-coordinate Ru complex with double agostic interactions has a higher ground state.
Author: Daniel Jason Fox
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Category :
Languages : en
Pages : 284
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Author: Jubo Zhang
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Category :
Languages : en
Pages : 232
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Keywords: Amidinate Complex, PCP Ligand, Ruthenium Amido, Imine Metathesis, Ruthenium Carbene, Platinum Amido.
Author: Morgan C. MacInnis
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Languages : en
Pages : 504
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ABSTRACT continued: These transfer hydrogenation studies are among the first catalytic studies of silyl-pincer complexes and establish [R-PSiP]M species as viable candidates for catalysis. The synthesis and reactivity of 4- and 5-coordinate RuII complexes featuring the [Cy-PSiP] ligand were explored. Reaction of [Cy-PSiP]H with [(p-cymene)RuCl2]2 in the presence of NEt3 and PCy3 resulted in the formation of ([Cy-PSiP]RuCl)2, which serves as a precursor to a series of unprecedented 4-coordinate, formally 14-electron [Cy-PSiP]RuX (X = NHAr, N(SiMe3)2, OtBu) complexes that feature an unusual trigonal pyramidal geometry at Ru. The reactivity of these novel diamagnetic complexes is described, including the reaction of [Cy-PSiP]RuOtBu with amine-boranes resulting in the formation of rare bis(?-BH) complexes. Computational studies confirmed the key role of the strongly ?-donating silyl group of the Cy-PSiP ligand in facilitating the synthesis of such low-coordinate Ru species and enforcing the unusual trigonal pyramidal geometry. The mechanism of ammonia-borane activation was also examined computationally. Lastly, the synthesis and structural characterization of PdII complexes supported by the pincer-like bis(amino)phosphido ligand [?3-(2-Me2NC6H4)2P]- ([NPN]) is described. Examples of ?1-, ?2-, and ?3-NPN coordination to Pd are described, as is the catalytic activity of ([NPN]PdX)2 (X = Cl, OAc, OTf) complexes in the Heck olefin arylation reaction. In an effort to discourage the formation of phosphido-bridged dinuclear complexes, pre-coordination of the Lewis acid BPh3 to [NPN] was pursued. Upon reaction of [N(P?BPh3)N]K with [PdCl(C3H5)]2, the ?1-allyl complex [?3-N(P?BPh3)N]Pd(?1-C3H5) was isolated, which establishes the coordination of a Lewis acid to the phosphido donor of the [NPN] ligand as a viable strategy for encouraging the formation of mononuclear ?3-NPN complexes.
Author: Richard Ira Michelman
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Category :
Languages : en
Pages : 344
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Author: Michael A. Dewey
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Category : Amino compounds
Languages : en
Pages : 366
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Author: Sean Clapham
Publisher:
ISBN: 9780494397831
Category :
Languages : en
Pages : 404
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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.
Author: Shun-Ichi Murahashi
Publisher: John Wiley & Sons
ISBN: 3527605797
Category : Science
Languages : en
Pages : 398
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In this comprehensive book, one of the leading experts, Shun-Ichi Murahashi, presents all the important facets of modern synthetic chemistry using Ruthenium, ranging from hydrogenation to metathesis. In 14 contributions, written by an international authorship, readers will find all the information they need about this fascinating and extraordinary chemistry. The result is a high quality information source and a indispensable reading for everyone working in organometallic chemistry. From the contents: Introduction (S.-I. Murahashi) Hydrogenation and Transfer Hydrogenation (M. Kitamura and R. Noyori) Oxidations (S.-I. Murahashi and N. Komiya) Carbon-Carbon Bond Formations via Ruthenacycle Intermediates (K. Itoh) Carbon-Carbon Bond Formation via pi-Allylruthenium Intermediates (T. Mitsudo) Olefin Metathesis (R. H. Grubbs) Cyclopropanation (H. Nishiyama) Nucleophilic Addition to Alkynes and Reactions via Vinylidene Intermediates (P. Dixneuf) Reactions via C-H Activation (N. Chatani) Lewis Acid Reactions (E. P. Kundig) Reactions with CO and CO2 (T. Mitsudo) Isomerization of Organic Substrates Catalyzed by Ruthenium Complexes (H. Suzuki) Radical Reactions (H. Nagashima) Bond Cleavage Reactions (S. Komiya)
