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Theoretical investigation on the effect of the ligand on bis-silylation of C(sp)-C(sp) by Ni complexes.

ABSTRACT: Density functional theory is used to study the bis-silylation of alkyne catalysed by a transition metal nickel-organic complex. The active catalyst, organic ligand, reaction mechanism, and rate-determining step were discussed with regard to dynamics and thermodynamics. COD or SIPr (COD = cyclooctadiene, SIPr = 1,3-bis(2,6-diisopropyl-phenyl)-4,5-dihydroimidazol-2-ylidene) coordination with Ni will greatly reduce the energy barrier of the Si-Si insertion step, that is, ΔΔG reaches 15.5 kcal mol^-1. Furthermore, the structure of alkynes will change the energy barrier of the alkyne insertion step.

SUBMITTER: Hui L

PROVIDER: S-EPMC8979076 | biostudies-literature | 2021 Dec

REPOSITORIES: biostudies-literature

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Theoretical investigation on the effect of the ligand on bis-silylation of C(sp)-C(sp) by Ni complexes.

Hui Li L Yuhan He H Jiaqi Wang W

RSC advances 20211201 2

Density functional theory is used to study the bis-silylation of alkyne catalysed by a transition metal nickel-organic complex. The active catalyst, organic ligand, reaction mechanism, and rate-determining step were discussed with regard to dynamics and thermodynamics. COD or SIPr (COD = cyclooctadiene, SIPr = 1,3-bis(2,6-diisopropyl-phenyl)-4,5-dihydroimidazol-2-ylidene) coordination with Ni will greatly reduce the energy barrier of the Si-Si insertion step, that is, ΔΔ<i>G</i> reaches 15.5 kca ...[more]

PMID: 35425119

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Project description:In this work, we report solvent-induced complexation properties of a new N2S2 tetradentate bis-thiosemicarbazone ligand (H2LI), prepared by the condensation of 4-phenylthiosemicarbazide with bis-aldehyde, namely 2,2'-(ethane-1,2-diylbis(oxy)dibenzaldehyde, towards nickel(II). Using ethanol as a reaction medium allowed the isolation of a discrete mononuclear homoleptic complex [NiLI] (1), for which its crystal structure contains three independent molecules, namely 1-I, 1-II, and 1-III, in the asymmetric unit. The doubly deprotonated ligand LI in the structure of 1 is coordinated in a cis-manner through the azomethine nitrogen atoms and the thiocarbonyl sulfur atoms. The coordination geometry around metal centers in all the three crystallographically independent molecules of 1 is best described as the seesaw structure. Interestingly, using methanol as a reaction medium in the same synthesis allowed for the isolation of a discrete mononuclear homoleptic complex [Ni(LII)2] (2), where LII is a monodeprotonated ligand 2-(2-(2-(2-(dimethoxymethyl)phenoxy)ethoxy)benzylidene)-N-phenylhydrazine-1-carbothioamide (HLII). The ligand LII was formed in situ from the reaction of LI with methanol upon coordination to the metal center under synthetic conditions. In the structure of 2, two ligands LII are coordinated in a trans-manner through the azomethine nitrogen atom and the thiocarbonyl sulfur atom, also yielding a seesaw coordination geometry around the metal center. The charge and energy decomposition scheme ETS-NOCV allows for the conclusion that both structures are stabilized by a bunch of London dispersion-driven intermolecular interactions, including predominantly N-H∙∙∙S and N-H∙∙∙O hydrogen bonds in 1 and 2, respectively; they are further augmented by less typical C-H∙∙∙X (where X = S, N, O, π), CH∙∙∙HC, π∙∙∙π stacking and the most striking, attractive long-range intermolecular C-H∙∙∙Ni preagostic interactions. The latter are found to be determined by both stabilizing Coulomb forces and an exchange-correlation contribution as revealed by the IQA energy decomposition scheme. Interestingly, the analogous long-range C-H∙∙∙S interactions are characterized by a repulsive Coulomb contribution and the prevailing attractive exchange-correlation constituent. The electron density of the delocalized bonds (EDDB) method shows that the nickel(II) atom shares only ~0.8|e| due to the σ-conjugation with the adjacent in-plane atoms, demonstrating a very weak σ-metalloaromatic character.

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Theoretical investigation on the effect of the ligand on bis-silylation of C(sp)-C(sp) by Ni complexes.

Publications

Theoretical investigation on the effect of the ligand on bis-silylation of C(sp)-C(sp) by Ni complexes.

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