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Manganese and iron PCP pincer complexes - the influence of sterics on structure and reactivity.
Dalton Trans
October 2021
Institute of Applied Synthetic Chemistry, Vienna University of Technology, Getreidemarkt 9, A-1060 Vienna, Austria.
The syntheses of various manganese and iron PCP pincer complexes a solvothermal oxidative addition methodology is described. Upon reacting [Mn(CO)] with the ligands (P(C-Br)P-iPr) (1a) and (P(C-Br)P-iPr) (1b), Mn(I) PCP pincer complexes [Mn(PCP-iPr)(CO)] (2a) and [Mn(-PCP-iPr)(CO)] (2b) were obtained. Protonation of 2a with HBF·EtO led to the formation of [Mn(κ,,-P(CH)P-iPr)(CO)]BF (3) featuring an η-C-H agostic bond.
View Article and Find Full Text PDFThe synthesis of new Schrock-Osborn Rh(i) pre-catalysts with -substituted DPEphos ligands, [Rh(DPEphos-R)(NBD)][BAr ] [R = Me, OMe, Pr; Ar = 3,5-(CF)CH], is described. Along with the previously reported R = H variant, variable temperature H NMR spectroscopic and single-crystal X-ray diffraction studies show that these all have axial (C-H)⋯Rh anagostic interactions relative to the d pseudo square planar metal centres, that also result in corresponding downfield chemical shifts. Analysis by NBO, QTAIM and NCI methods shows these to be only very weak C-H⋯Rh bonding interactions, the magnitudes of which do not correlate with the observed chemical shifts.
View Article and Find Full Text PDFCarbon-13 NMR Chemical Shift: A Descriptor for Electronic Structure and Reactivity of Organometallic Compounds.
Acc Chem Res
August 2019
ICGM, Université Montpellier, CNRS, ENSCM, 34095 Montpellier , France.
Article Synopsis
- Metal-bonded carbon atoms in compounds like metal-alkyl and metal-carbene show significantly more deshielded isotropic chemical shifts compared to typical organic compounds (alkanes, alkenes, and alkynes).
- The isotropic chemical shift is an average measurement that reflects the electronic environment, and solid-state NMR spectroscopy can provide deeper insights into the electronic structure via the chemical shift tensor.
- This phenomenon of deshielding, particularly noted in organometallics, relates to interactions between different types of molecular orbitals, indicating reactivity patterns and characterizing the nature of the bonding in these compounds.
Oxidation State Dependent Coordination Modes: Accessing an Amidate-Supported Nickel(I) δ-bis(C-H) Agostic Complex.
Angew Chem Int Ed Engl
October 2016
Department of Chemistry, The University of British Columbia, Vancouver, BC, V6T 1Z1, Canada.
Amidate-supported two- and three-coordinate Ni complexes were synthesized by reduction of the corresponding Ni precursors. A dramatic change in binding mode is observed upon reduction from Ni to Ni . The Ni derivatives include an unprecedented Ni bis(C-H) agostic complex and a two-coordinate Ni complex.
View Article and Find Full Text PDFCatalytic and stoichiometric reactivity of β-silylamido agostic complex of Mo: intermediacy of a silanimine complex and applications to multicomponent coupling.
J Am Chem Soc
May 2011
Department of Chemistry, Brock University, St Catharines, Ontario L2S 3A1, Canada.
The reaction of complex (ArN═)(2)Mo(PMe(3))(3) (Ar = 2,6-diisopropylphenyl) with PhSiH(3) gives the β-agostic NSi-H···M silyamido complex (ArN═)Mo(SiH(2)Ph)(PMe(3))(η(3)-ArN-SiHPh-H) (3) as the first product. 3 decomposes in the mother liquor to a mixture of hydride compounds, including complex {η(3)-SiH(Ph)-N(Ar)-SiHPh-H···}MoH(3)(PMe(3))(3) characterized by NMR. Compound 3 was obtained on preparative scale by reacting (ArN═)(2)Mo(PMe(3))(3) with 2 equiv of PhSiH(3) under N(2) purging and characterized by multinuclear NMR, IR, and X-ray diffraction.
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