Unknown

Dataset Information

0

Facile Access to Dative, Single, and Double Silicon-Metal Bonds Through M-Cl Insertion Reactions of Base-Stabilized SiII Cations.

ABSTRACT: Silicon(II) cations can offer fascinating reactivity patterns due to their unique electronic structure: a lone pair of electrons, two empty p orbitals and a positive charge combined on a single silicon center. We now report the facile insertion of N-heterocyclic carbene (NHC)-stabilized silyliumylidene ions into M-Cl bonds (M=Ru, Rh), forming a series of novel chlorosilylene transition-metal complexes. Theoretical investigations revealed a reaction mechanism in which the insertion into the M-Cl bond with concomitant 1,2-migration of a silicon-bound NHC to the transition metal takes place after formation of an initial silyliumylidene transition-metal complex. The mechanism could be verified experimentally through characterization of the intermediate complexes. Furthermore, the obtained chlorosilylene complexes can be conveniently utilized as synthons to access Si-M and Si=M bonding motifs bonds through reductive dehalogenation.

SUBMITTER: Frisch P 

PROVIDER: S-EPMC7318344 | biostudies-literature | 2020 May

REPOSITORIES: biostudies-literature

Json Xml
altmetric image

Publications

Facile Access to Dative, Single, and Double Silicon-Metal Bonds Through M-Cl Insertion Reactions of Base-Stabilized Si<sup>II</sup> Cations.

Frisch Philipp P   Szilvási Tibor T   Inoue Shigeyoshi S  

Chemistry (Weinheim an der Bergstrasse, Germany) 20200428 28

Silicon(II) cations can offer fascinating reactivity patterns due to their unique electronic structure: a lone pair of electrons, two empty p orbitals and a positive charge combined on a single silicon center. We now report the facile insertion of N-heterocyclic carbene (NHC)-stabilized silyliumylidene ions into M-Cl bonds (M=Ru, Rh), forming a series of novel chlorosilylene transition-metal complexes. Theoretical investigations revealed a reaction mechanism in which the insertion into the M-Cl  ...[more]

Similar Datasets

Unknown New Hindered Amide Base for Aryne Insertion into Si-P, Si-S, Si-N, and C-C Bonds.
| S-EPMC6458107 | biostudies-literature
Unknown Spirocyclic germanes via transannular insertion reactions of vinyl germylenes into Si-Si bonds.
| S-EPMC5946683 | biostudies-other
Unknown Surprisingly facile CO2 insertion into cobalt alkoxide bonds: A theoretical investigation.
| S-EPMC4578342 | biostudies-literature
Unknown Enantioselective Diarylcarbene Insertion into Si-H Bonds Induced by Electronic Properties of the Carbenes.
| S-EPMC7605718 | biostudies-literature
Unknown <sup>29</sup>Si NMR Chemical Shifts in Crystalline and Amorphous Silicon Nitrides.
| S-EPMC6164960 | biostudies-literature
Unknown Enantioselective Si-H Insertion Reactions of Diarylcarbenes for the Synthesis of Silicon-Stereogenic Silanes.
| S-EPMC7747653 | biostudies-literature
Unknown Serpentine alteration as source of high dissolved silicon and elevated δ<sup>30</sup>Si values to the marine Si cycle.
| S-EPMC7550359 | biostudies-literature
Unknown Solution Phase Reactivity of Dibenzo[c,e][1,2]azaborinine: Activation and Insertion into Si-E Single Bonds (E=H, OSi(CH<sub>3</sub> )<sub>3</sub> , F, Cl) by a BN-Aryne.
| S-EPMC9299606 | biostudies-literature
Unknown A trigonal coordination of Au(I) phosphane complexes stabilized by O-H <sup><b>⋯</b></sup> X (X = Cl<sup>-</sup>, Br<sup>-</sup>, I<sup>-</sup>) interactions.
| S-EPMC8550744 | biostudies-literature
Unknown Cyclic Octamer of Hydroxyl-functionalized Cations with Net Charge Q=+8e Kinetically Stabilized by a 'Molecular Island' of Cooperative Hydrogen Bonds.
| S-EPMC7702028 | biostudies-literature