377 research outputs found
A Two-Coordinate Nickel Imido Complex That Effects C−H Amination
An exceptionally low coordinate nickel imido complex, (IPr*)Ni═N(dmp) (2) (dmp = 2,6-dimesitylphenyl), has been prepared by the elimination of N_2 from a bulky aryl azide in its reaction with (IPr*)Ni(η^6-C_7H_8) (1). The solid-state structure of 2 features two-coordinate nickel with a linear C−Ni−N core and a short Ni−N distance, both indicative of multiple-bond character. Computational studies using density functional theory showed a Ni═N bond dominated by Ni(dπ)−N(pπ) interactions, resulting in two nearly degenerate singly occupied molecular orbitals (SOMOs) that are Ni−N π* in character. Reaction of 2 with CO resulted in nitrene-group transfer to form (dmp)NCO and (IPr*)Ni(CO)_3 (3). Net C−H insertion was observed in the reaction of 2 with ethene, forming the vinylamine (dmp)NH(CH═CH_2) (5) via an azanickelacyclobutane intermediate, (IPr*)Ni{N,C:κ^2-N(dmp)CH_2CH_2} (4)
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[Review] Chemistry of Advanced Materials: An Overview
This article reviews the book "Chemistry of Advanced Materials: An Overview," edited by Leonard V. Interrante and Mark J. Hampden-Smith
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Calculation of a Methane C-H Oxidative Addition Trajectory: Comparison to Experiment and Methane Activation by High-Valent Complexes
Article discussing research on the calculation of methane C-H oxidative addition trajectory and a comparison to experiment and methane activation by high-valent complexes
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Transition Metal Imido Complexes
Article discussing a wide range of transition metal imido (TMI) complexes using ab initio molecular orbital (MO) calculations
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Methane Activation by Group IVB Imido Complexes
Article discussing an ab initio study of methane activation by group IVB imido complexes
Ligand Lone-Pair Influence on Hydrocarbon C-H Activation: A Computational Perspective
Mid to late transition metal complexes that break hydrocarbon C-H bonds by transferring the hydrogen to a heteroatom ligand while forming a metal-alkyl bond offer a promising strategy for C-H activation. Here we report a density functional (B3LYP, M06, and X3LYP) analysis of
cis-(acac)_2MX and TpM(L)X (M=Ir, Ru, Os, and Rh; acac=acetylacetonate, Tp=tris(pyrazolyl)-borate; X=CH_3, OH, OMe, NH_2, and NMe_2) systems for methane C-H bond activation reaction kinetics and thermodynamics.We address the importance of whether a ligand lone pair provides an
intrinsic kinetic advantage through possible electronic d_π-p_π repulsions for M-OR and M-NR_2 systems versus M-CH_3 systems. This involves understanding the energetic impact of the X ligand group on ligand loss, C-H bond coordination, and C-H bond cleavage steps as well as understanding how the nucleophilicity of the ligand X group, the electrophilicity of the transition metal center, and cis-ligand stabilization effect influence each of these steps.We also explore how spectator ligands and second- versus third-row transition metal centers impact the energetics of each of these C-H activation steps
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Modeling the Deposition of Metal Atoms on a p-Type Organometallic Conductor: Implications for Stability and Electron Transfer
Article discussing modeling the deposition of metal atoms on a p-Type organometallic conductor and implications for stability and electron transfer
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Principal Resonance Contributors to High-Valent, Transition-Metal Alkylidene Complexes
Article discussing principal resonance contributors to high-valent, transition-metal alkylidene complexes
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Carbon-Hydrogen Bond Activation by Titanium Imido Complexes. Computational Evidence for the Role of Alkane Adducts in Selective C-H Activation
This article reports calculations that probe the role of R (hydrocarbon) and R' (ligand substituent) effects on the reaction coordinate for C-H activation
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