Organometallic Reagents

doi:10.1002/9780470651568.ch6

Cited by 3 publications

(2 citation statements)

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“…All reactions were performed in an inert nitrogen atmosphere while using standard Schlenk techniques. (Bu 4 N)[10-MeS-7,8-C 2 B 9 H 11 ], (Bu 4 N)[9-MeS-7,8-C 2 B 9 H 11 ], and [Ni(acac) 2 ] 3 were prepared as described in the literature [42][43][44]. Anhydrous tetrahydrofuran was prepared by using the standard procedure [45].…”

Section: General Considerationsmentioning

confidence: 99%

Synthesis and Structure of Methylsulfanyl Derivatives of Nickel Bis(Dicarbollide)

et al. 2019

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Symmetrically and unsymmetrically substituted methylsulfanyl derivatives of nickel(III) bis(dicarbollide) (Bu4N)[8,8′-(MeS)2-3,3′-Ni(1,2-C2B9H10)2], (Bu4N)[4,4′-(MeS)2-3,3′-Ni(1,2-C2B9H10)2], and (Bu4N)[4,7′-(MeS)2-3,3′-Ni(1,2-C2B9H10)2] were synthesized, starting from [Ni(acac)2]3 and the corresponding methylsulfanyl derivatives of nido-carborane (Bu4N)[10-MeS-7,8-C2B9H11] and (Bu4N)[10-MeS-7,8-C2B9H11]. Structures of the synthesized metallacarboranes were studied by single-crystal X-ray diffraction and quantum chemical calculations. The symmetrically substituted 8,8′-isomer adopts transoid conformation stabilized by two pairs of intramolecular C–H···S hydrogen bonds between the dicarbollide ligands. The unsymmetrically substituted 4,7′-isomer adopts gauche conformation, which is stabilized by two nonequivalent C–H···S hydrogen bonds and one short chalcogen B–H···S bond (2.53 Å, −1.4 kcal/mol). The gauche conformation was found to be also preferred for the 4,7′-isomer.

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Section: General Considerationsmentioning

confidence: 99%

Synthesis and Structure of Methylsulfanyl Derivatives of Nickel Bis(Dicarbollide)

et al. 2019

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“…The first known and most stable bis(1,5-cyclooctadiene)metal derivative of a first row transition metal is the nickel derivative (η 2,2 -C 8 H 12 ) 2 Ni, readily synthesized from the reaction of Ni(acac) 2 (acac = acetylacetonate) or NiX 2 (X = halide) with 1,5-cyclooctadiene in the presence of a reducing agent such as iPrMgBr, Et 3 Al, iBu 2 AlH, or nBu 2 Mg (Figure ). The stability of (η 2,2 -C 8 H 12 ) 2 Ni can be related to the favored 18-electron configuration − of the central nickel atom.…”

Section: Introductionmentioning

confidence: 99%

Carbon–Hydrogen Activation in Zerovalent Bis(1,5-cyclooctadiene) Complexes of the First Row Transition Metals: A Theoretical Study

Feng

Xie

et al. 2018

J. Phys. Chem. A

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Stepwise interaction of first row transition metal atoms with 1,5-cyclooctadiene to give (CH)M complexes is studied using the M06-L/DZP density functional method. The experimentally known (CH)Ni is the thermodynamically most favorable complex, with a predicted geometry consistent with its experimental structure as determined by X-ray crystallography. The other transition metal atoms from scandium to zinc also interact exothermically with 1,5-cyclooctadiene to give (CH)M derivatives, but these exhibit lower symmetry than the S symmetry exhibited by (CH)Ni. Carbon-hydrogen activation of CH groups in a CH ligand is predicted for most systems. Thus, conversion of (η-CH)M to (η-CH)(η-CH)M, through a hydride intermediate (η-CH)(η-CH)MH, is predicted for scandium, vanadium, chromium, manganese, and cobalt. For titanium with a low-lying empty orbital, further C-H activation through a hydride intermediate (η-CH)(η-CH)TiH is predicted, leading ultimately to (η-CH)(η-CH)Ti, in which the hexahapto η-CH ligand is shown by NICS to be aromatic. These two C-H activation processes on a titanium center represent the dehydrogenation of 1,5-cyclooctadiene to 1,3,5-cyclooctatriene with the second 1,5-cyclooctadiene ligand as the hydrogen acceptor. For zinc C-H activation terminates at (η-CH)(CH)ZnH, which has a C-Zn-H three-center bond. No energetically favorable C-H activation processes are predicted for the iron, nickel, and copper (η-CH)M derivatives.

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Group VI Metal Complexes of Carbon Monoxide and Isocyanides

Fischer

2022

Comprehensive Organometallic Chemistry IV

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Organometallic Reagents

Cited by 3 publications

References 68 publications

Synthesis and Structure of Methylsulfanyl Derivatives of Nickel Bis(Dicarbollide)

Synthesis and Structure of Methylsulfanyl Derivatives of Nickel Bis(Dicarbollide)

Carbon–Hydrogen Activation in Zerovalent Bis(1,5-cyclooctadiene) Complexes of the First Row Transition Metals: A Theoretical Study

Group VI Metal Complexes of Carbon Monoxide and Isocyanides

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