Amidinate-Stabilized Group 9 Metal-Silicon(I) Dimer and -Silylene Complexes.

@article{Khoo2015AmidinateStabilizedG9,
  title={Amidinate-Stabilized Group 9 Metal-Silicon(I) Dimer and -Silylene Complexes.},
  author={Sabrina Khoo and Hui-Xian Yeong and Yongxin Li and Rakesh Ganguly and Cheuk-Wai So},
  journal={Inorganic chemistry},
  year={2015},
  volume={54 20},
  pages={
          9968-75
        }
}
The coordination chemistry of the amidinate-stabilized silicon(I) dimer toward group 9 metal complexes is described. The reaction of [LSi:]2 (1, L = PhC(NtBu)2) with [Ir(cod)Cl]2 (cod = 1,5-cyclooctadiene) in toluene at ambient temperature afforded the base-stabilized silicon(I) dimer-iridium complex [LSi{Ir(cod)-μ-Cl-Ir(cod)}SiL][(cod)IrCl2] (2). In contrast, the reaction of 1 with [Rh(cod)Cl]2 in toluene at ambient temperature afforded a mixture of the amidinate-stabilized silicon(I) dimer… 
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References

SHOWING 1-10 OF 49 REFERENCES
N-Heterocyclic Silylene (NHSi) Rhodium and Iridium Complexes: Synthesis, Structure, Reactivity, and Catalytic Ability
Reaction of the zwitterionic N-heterocyclic silylene (NHSi) 1 L′Si: (L′ = [HC(CMeNAr)(C(CH2)NAr)], Ar = 2,6-iPr2C6H3) with HCl at low temperatures affords the kinetically stable 1,4-addition product
From a zwitterionic phosphasilene to base stabilized silyliumylidene-phosphide and bis(silylene) complexes.
TLDR
Density functional theory calculations of the reaction mechanisms showed that the migration of the TMS group in the case of platinum and palladium was induced by the oxidative addition of the transition metal into the silicon-silicon bond.
Facile access to silicon-functionalized bis-silylene titanium(II) complexes.
TLDR
All complexes were fully characterized and the structures of 3 and 4 elucidated by single-crystal X-ray diffraction analysis and DFT calculations of complexes 3-5 were also carried out to assess the nature of the titanium-silicon bonds.
Electron-rich N-heterocyclic silylene (NHSi)-iron complexes: synthesis, structures, and catalytic ability of an isolable hydridosilylene-iron complex.
TLDR
The first electron-rich N-heterocyclic silylene (NHSi)-iron(0) complexes are reported, and for the first time, the catalytic activity of a Si(II) hydride complex was investigated.
A silyliumylidene cation stabilized by an amidinate ligand and 4-dimethylaminopyridine.
TLDR
The synthesis and reactivity of a silyliumylidene cation stabilized by an amidinate ligand and 4-dimethylaminopyridine (DMAP) are described and compounds 2, 3, and 5 have been characterized by X-ray crystallography.
Elucidating the effect of the nucleophilicity of the silyl group in the reduction of CO2 to CO mediated by silyl-copper(I) complexes.
TLDR
The silyl moieties of complexes 2 and 3, containing electron-donating groups (i.e., OtBu and OH) at the silicon centers, are more nucleophilic than that of compound 4 and 5, bearing a hydride and the electron-withdrawing group OC6F5 at the Silicon centers, respectively.
Synthesis and characterization of an amidinate-stabilized cis-1,2-disilylenylethene [cis-LSi{C(Ph)=C(H)}SiL] and a singlet delocalized biradicaloid [LSi(μ(2)-C(2)Ph(2))(2)SiL].
TLDR
X-ray crystallography and DFT calculations of 3 show that the singlet biradicals are stabilized by the amidinate ligand and the delocalization within the "Si(μ(2)-C(2)Ph(2))( 2)Si" six-membered ring.
From bis(silylene) and bis(germylene) pincer-type nickel(II) complexes to isolable intermediates of the nickel-catalyzed Sonogashira cross-coupling reaction.
TLDR
The results reveal a general reaction mechanism for the Ni-based Sonogashira coupling and broaden the application of metallylenes as strong σ-donor ligands for catalytic transformations.
Synthesis and structure of PNP-supported iridium silyl and silylene complexes: catalytic hydrosilation of alkenes.
TLDR
Complex 20 was found to be catalytically active for the hydrosilation of alkenes, which is consistent with its intermediacy in the catalytic cycle and anti-Markovnikov regioselectivity with an array of alkene substrates.
Synthesis and characterization of cationic rhodium complexes with stable silylenes
Two cationic rhodium(I)−tetrasilylene complexes, (4; BArF = tetrakis[3,5-bis(trifluoromethyl)phenyl]borate) and (5), were prepared from [Rh(cod)2]BArF and
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