- Novel clamp metal complex and application thereof
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The invention discloses a method for preparing a novel clamp-shaped complex and application of the novel clamp-shaped complex in the reaction of catalytic hydrogenation of carboxylic acid ester compounds to produce corresponding alcohols and reaction of carbon dioxide catalytic hydrogenation to form formamide compounds. Carboxylic acid esters and hydrogen as raw materials or carbon dioxide, hydrogen and amine compounds as raw materials are reacted in an organic solvent condition or a solvent-free condition in the presence of a transition metal complex as a catalyst to respectively form the corresponding alcohol compounds and/or corresponding formamide compounds. The method has the advantages of being high in reaction efficiency, good in selectivity, mild in conditions, economical, environmentally-friendly, and simple in operation, and has good promotion and application prospects.
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- Synthesis and characterization of rhenium(III) complexes with (Ph2PCH2CH2)2NR diphosphinoamine ligands
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The synthesis and characterization of a new series of neutral, six-coordinated compounds [ReIIIX3(PNPR)], where X is Cl or Br and PNPR is a diphosphinoamine having the general formula (Ph2PCH2CH2)2NR (R = H, CH3, CH2CH3, CH2CH2CH3, CH2CH2CH2CH3 and CH2CH2OCH3) are reported. Stable [ReIIIX3(PNPR)] complexes were synthesized, in variable yields, starting from precursors where the metal was in different oxidation states (iii and v), by ligand-exchange and/or redox-substitution reactions. The compounds were characterized by elemental analysis, proton NMR spectroscopy, cyclic voltammetry, UV/vis spectroscopy, positive-ion electrospray ionization mass spectrometry (ESI(+)-MS) and X-ray diffraction analysis. Although the formulation of the complexes allows either meridional or facial isomers, the latter arrangement was prevalent both in the solid and solution states. Only [ReCl3(PNPH)] showed a meridional configuration both in solution and in the crystalline state. [ReBr3(PNPme)] prefers the meridional configuration in the crystalline state and the facial one in solution. While ESI(+)-MS and voltammetric data seem to indicate some dependency from the nature of the alkyl substituent at the nitrogen, the available structural data of the complexes show only slight differences both for angles and bond lengths upon change of the alkyl chain tethered to the nitrogen.
- Salvarese, Nicola,Refosco, Fiorenzo,Seraglia, Roberta,Roverso, Marco,Dolmella, Alessandro,Bolzati, Cristina
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p. 9180 - 9191
(2017/07/24)
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- Scope and limitations of the preparation of aminophosphines R-NH(CH2CH2PPH2) and aminodiphosphines R-N(CH2CH2PPH2)2 via Michael addition of amines to vinylphosphines
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The addition of a range of amines to vinyldiphenylphosphine oxide was examined under different reaction conditions. The methodology provides mixed phosphorus-nitrogen donor ligands R-NH(CH2CH2PPh2) 3 and R-N(CH2CH2PPh2)2 4, which could be prepared in high yields and purity in two simple steps. Labelling study revealed a non-concerted mechanism and the X-ray crystal structure of 1e is reported.
- Rahman,Steed,Hii
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p. 1320 - 1326
(2007/10/03)
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