Synthesis and Reactivity of Ruthenium and Platinum Amido and Carbene Complexes: Application Toward Carbon-Nitrogen Bond Forming Reactions PDF Download
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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.
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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: Jubo Zhang
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Languages : en
Pages : 232
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Keywords: Amidinate Complex, PCP Ligand, Ruthenium Amido, Imine Metathesis, Ruthenium Carbene, Platinum Amido.
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Languages : en
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Author: David Michael Conner
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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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Isolated and fully characterized complexes of late transition metals in low oxidation states possessing amido and alkoxo ligands are relatively rare. These ligands often exhibit nucleophilic and/or basic reactivity. This reactivity is due, at least in part, to the disruption of ligand to metal à â'Ơ-bonding. Reports of early transition metals with low d-electron counts with imido ligands facilitating C-H activation suggest that if later transition metals with amido or aryloxo ligands can be isolated, C-H activation reactivity may be observed. Ruthenium(II) complexes that catalyze the H/D exchange of N-H and O-H protons at anilido and hydroxo ligands, respectively, with deuterated solvents have been reported, and studies of related systems could shed significant light on C-H activation in these types of reactions. Observing changes in the rate of C-H activation based on specific changes to transition metal complexes could give insight into the creation of highly active C-H activation catalysts. Presented here are synthetic efforts toward late transition metal complexes with formally anionic heteroatomic ligands. The synthesis and initial characterization of [EpRu(Cl)(PPh3)(NCMe)][Cl], [EpRu(py)2Cl][Cl], [EpRu(py)2Cl][Cl], [EpRu(OHMe)(PMe3)(Cl)][BArÃØâ'Ơâ"Ø4] are reported {Ep = 1,1,1-tris(pyrazolyl)ethane, py = N-pyridine, ArÃØâ'Ơâ"Ø = 3,5-(CF3)-C6H3}. The lack of solubility yielded these complexes ineffective for further synthetic manipulation. Additionally presented is the synthesis and characterization of (tbpy)Pt(Me)2(I)2 and (tbpy)Pt(Me)(NHPh)(I)2 (tbpy = 4,4ÃØâ'Ơâ"Ø-tert-butyl-2,2ÃØâ'Ơâ"Ø-bipyridine). Attempted syntheses of (tbpy)Pt(NHPh)2(I)2 and (tbpy)Pt(Cl)(NHPh)(I)2 are also reported. Initial reactivity of (tbpy)Pt(Me)2(I)2 and the decomposition of (tbpy)Pt(Me)(NHPh)(I)2 are further re.
Author: Taisuke Sumiyoshi
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Languages : en
Pages : 114
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Keywords: ruthenium, platinum, non-dative heteroatomic ligand.
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 Ronald Willis
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Languages : en
Pages : 524
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Author: Yan Li
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ISBN: 9781361426203
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Languages : en
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