481 research outputs found
A Two-Coordinate Nickel Imido Complex That Effects CāH Amination
An exceptionally low coordinate nickel imido complex, (IPr*)NiāN(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(Ī·^6-C_7H_8) (1). The solid-state structure of 2 features two-coordinate nickel with a linear CāNiāN core and a short NiāN distance, both indicative of multiple-bond character. Computational studies using density functional theory showed a NiāN bond dominated by Ni(dĻ)āN(pĻ) interactions, resulting in two nearly degenerate singly occupied molecular orbitals (SOMOs) that are NiāN Ļ* in character. Reaction of 2 with CO resulted in nitrene-group transfer to form (dmp)NCO and (IPr*)Ni(CO)_3 (3). Net CāH insertion was observed in the reaction of 2 with ethene, forming the vinylamine (dmp)NH(CHāCH_2) (5) via an azanickelacyclobutane intermediate, (IPr*)Ni{N,C:Īŗ^2-N(dmp)CH_2CH_2} (4)
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Molecular Modeling of Vanadium-Oxo Complexes. A Comparison of Quantum and Classical Methods
This article discusses molecular modeling of vanadium-oxo complexes and a comparison of quantum and classical methods
Angular Forces Around Transition Metals in Biomolecules
Quantum-mechanical analysis based on an exact sum rule is used to extract an
semiclassical angle-dependent energy function for transition metal ions in
biomolecules. The angular dependence is simple but different from existing
classical potentials. Comparison of predicted energies with a
computer-generated database shows that the semiclassical energy function is
remarkably accurate, and that its angular dependence is optimal.Comment: Tex file plus 4 postscript figure
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Group-Transfer Reactions of Nickel-Carbene and -Nitrene Complexes with Organoazides and Nitrous Oxide that Form New C=N, C=O, and N=N Bonds
This article discusses group-transfer reactions of nickel-carbene and -nitrene complexes with organoazides and nitrous oxide that form new C=N, C=O, and N=N bonds
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Reductive Elimination of Alkylamines from Low-Valent, Alkylpalladium(II) Amido Complexes
This article discusses reductive elimination of alkylamines from low-valent, alkylpalladium(II) amido complexes
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A Two-Coordinate Nickel Imido Complex That Effects C-H Amination
This article discusses a two-coordinate nickel imido complex that effects C-H amination
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