Reaction of a phosphinobenzylsilane compound with ruthenium complexes leads to C-H and/or Si-H activation. The new complex Ru{eta(2)-H-SiMe2CH(o-C(6)H(4))PPh2}2 (5) was isolated and X-ray, NMR and DFT studies reveal that 5 displays two agostic Si-H interactions and two carbon-metallated bonds.
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http://dx.doi.org/10.1039/b709408f | DOI Listing |
Inorg Chem
April 2022
Institut für Anorganische Chemie, Georg-August-Universität Göttingen, Tammannstraße 4, 37077 Göttingen, Germany.
The Si-H···Se contact in 1-mesitylselanyl-8-(dimethylsilyl)naphthalene (), which exhibits the spatial arrangement of a δ-agostic interaction from geometric considerations, was investigated. Is this just enforced by close 1,8-proximity or is this a favorable interaction? Charge density studies are best suited to investigate the exact origin of the interaction and to quantify the properties. Hence, they are most elucidating.
View Article and Find Full Text PDFChemistry
November 2020
Department of Chemistry, Graduate School of Engineering Science, Osaka University, Toyonaka, Osaka, 560-8531, Japan.
The rare-earth metal complexes Ln(L )[N(SiHMe ) ](thf) (Ln=La, Ce, Y; L =N,N''-bis(pentafluorophenyl)diethylenetriamine dianion) were synthesized by treating Ln[N(SiHMe ) ] (thf) with L H . The lanthanum and cerium derivatives are active catalysts for the hydrosilylation of benzophenone derivatives with HN(SiHMe ) . An amine-exchange reaction was revealed as a key step of the catalytic cycle, in which Ln-Si-H β-agostic interactions are proposed to promote insertion of the carbonyl moiety into the Si-H bond.
View Article and Find Full Text PDFInorg Chem
December 2019
Institut für Anorganische Chemie und Kristallographie , Universität Bremen, Leobener Straße 3 & 7 , 28359 Bremen , Germany.
A proximity enforcing diarylsilane ligand is reported, which gives rise to unusual Si-H···M interactions with the d metal ions Cu and Ag upon complexation. These interactions are studied in detail both experimentally and computationally and can be classified to be weakly agostic in nature for the Si-H···Cu interaction. The Si-H···Ag interaction has more signatures of an electrostatic contact.
View Article and Find Full Text PDFDalton Trans
October 2019
Centro de Investigaciones Químicas, IICBA, Universidad Autónoma del Estado de Morelos, Avenida Universidad 1001, Col. Chamilpa, Cuernavaca, Morelos C. P. 62209, Mexico and Department of Chemistry, Mississippi State University, Box 9573, Mississippi State, Mississippi 39762, USA.
In the solid state, the dinuclear iridium complex [μ-Cl-Ir(SiMeCH-o-CH)PPh], 1, is shown by X-ray diffraction to bear dibenzylsilylphosphine ligands in SiPSi tridentate coordination modes as well as chloride bridges. In CD solution, 1 dissociates into the 14-electron species [IrCl(SiMeCH-o-CH)PPh] prone to coordinate one or two L-type ligands such as PR (R = Cy, Ph, OEt), CO and CHCN giving rise to the corresponding mononuclear 16- or 18-electron complexes [IrCl(SiMeCH-o-CH)PPh(L)] (x = 1, 2) as evidenced by X-ray and NMR studies. The dinuclear structure is retained upon reaction with EtSiH which results in the formation of [μ-Cl,μ-H-Ir{(SiMeCH-o-CH)PPh}] with a bridging hydride.
View Article and Find Full Text PDFChemistry
August 2019
Instituto de Investigaciones Químicas (IIQ), Departamento de Química, Inorgánica, Centro de Innovación en Química Avanzada (ORFEO-CINCA), CSIC and Universidad de Sevilla, C/ Américo Vespucio 49, 41092, Sevilla, Spain.
Platinum complexes [Pt(NHC')(NHC)][BAr ] (in which NHC' denotes a cyclometalated N-heterocyclic carbene ligand, NHC) react with primary silanes RSiH to afford the cyclometalated platinum(II) silyl complexes [Pt(NHC-SiHR')(NHC)][BAr ] through a process that involves the formation of C-Si and Pt-Si bonds with concomitant extrusion of H . Low-temperature NMR studies indicate that the process proceeds through initial formation of the σ-SiH complexes [Pt(NHC')(NHC)(HSiH R)][BAr ], which are stable at temperatures below -10 °C. At higher temperatures, activation of one Si-H bond followed by a C-Si coupling reaction generates an agostic SiH platinum hydride derivative [Pt(H)(NHC'-SiH R)(NHC)][BAr ], which undergoes a second Si-H bond activation to afford the final products.
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