Reactivity of a silylsilylene bearing a functionalized diaminochlorosilyl substituent.

@article{Zhang2011ReactivityOA,
  title={Reactivity of a silylsilylene bearing a functionalized diaminochlorosilyl substituent.},
  author={Shuhua Zhang and Hui-Xian Yeong and Cheuk-Wai So},
  journal={Chemistry},
  year={2011},
  volume={17 12},
  pages={
          3490-9
        }
}
The reactivity of the silylsilylene [{PhC(NtBu)(2)}SiSi(Cl){(NtBu)(2)C(H)Ph}] (2) towards diphenylacetylene, azobenzene, 2,6-diisopropylphenyl azide, sulfur, and selenium is described. The reaction of 2 with one equivalent of azobenzene in toluene afforded compound 3, which is the first example of a 1,2-diaza-3,4-disilacyclobutane containing a pentacoordinate silicon center. The formation of 3 can be explained by a [1+2] cycloaddition of the divalent Si center in 2 with PhN=NPh to form a… 
64 Citations

Figures from this paper

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.
Stable silaimines with three- and four-coordinate silicon atoms.
TLDR
Compounds 5-9 are stable under inert atmosphere and were characterized by elemental analysis, NMR spectroscopy, and single-crystal X-ray studies.
Pentacoordinate Silicon Complexes with N-(2-pyridylmethyl)­salicylamide as a Dianionic (ONN′) Tridentate Chelator †‡
The title compound, N-(2-pyridylmethyl)salicylamide (1), was synthesized by ester aminolysis of methyl salicylate and 2-picolylamine. In the presence of triethylamine as a supporting base, the
Synthesis and Characterization of an Amidinate-Stabilized Siladithiocarboxylate and Its Germanium(II) Complex
The synthesis and characterization of the amidinate-stabilized potassium siladithiocarboxylate [{LSi(S)2}K(THF)2]2 (2, L = PhC(NBut)2) are described. Compound 2 was synthesized by the reaction of
Synthesis, structure and reactivity of a donor-stabilised silylene with a bulky bidentate benzamidinato ligand.
TLDR
Compounds (and the precursors and five-coordinate silicon(iv) complexes with an SiCl3N2 and SiCl2N3 skeleton, respectively) in the synthesis of silylene were characterised by elemental analyses, crystal structure analyses and multinuclear NMR spectroscopic studies in the solid state and in solution.
Synthesis and characterization of a singlet delocalized 2,4-diimino-1,3-disilacyclobutanediyl and a silylenylsilaimine.
TLDR
The results show that compound 2 possesses singlet biradicaloid character with an extensive electronic delocalization throughout the Si( 2)C(2) four-membered ring and exocyclic C=N bonds.
Chlorosilanes and 3,5‐Dimethylpyrazole: Multinuclear Complexes, Acetonitrile Insertion and 29Si NMR Chemical‐Shift Anisotropy Studies
The multinuclear silicon complexes [{H2ClSi(μ-pz*)2}2SiH2] (1) and [Cl2Si(μ-pzRR)2SiCl2] (2, R = Me; 3, R = Ph) were formed by the reaction of dichlorosilane (for 1) or hexachlorodisilane with
On the Reactivity of the Silylene PhC(NtBu)2SiNPh2 toward Organic Substrates
The reactivity studies of stable silylenes with organo isothiocyanates are so far not reported. In this manuscript we describe for the first time the reaction of the stable silylene LSiNPh2 (1) [L =
Chemistry of functionalized silylenes
Recent years have witnessed important developments in organosilicon chemistry, courtesy to the high yield access of stable monomeric chlorosilylene (LSiCl, L = PhC(NtBu)2) and N-heterocyclic carbene
Halogen-Exchange Reactions of Iminophosphonamido-Chlorosilylenes with Alkali Halides: Convenient Synthesis of Heavier Halosilylenes.
Halogen-substituted silylenes are an important building block for synthesizing silicon-based low-valent and multiple-bond species. However, the number of reports on heavier halosilylenes that contain
...
...

References

SHOWING 1-10 OF 90 REFERENCES
SYNTHESIS, STRUCTURE, AND REACTIVITY OF THE FIRST KINETICALLY STABILIZED SILANETHIONE
Diaryltetrathiasilolanes 2a,b, bearing bulky aryl groups such as 2,4,6-tris[bis(trimethylsilyl)methyl]phenyl (Tbt), mesityl (Mes), and 2,4,6-triisopropylphenyl (Tip), were obtained by thermal
Reactivity of a Zwitterionic Stable Silylene toward Halosilanes and Haloalkanes
The insertion of the thermally stable ylide-like silylene LSi: (1) {L = CH[(C═CH2)CMe][N(Ar)]2], Ar = 2,6-iPr2C6H3} into C−X and Si−X bonds of various small haloalkanes and halosilanes (MeI, PhCH2Br,
Synthesis and Reactivity of Three New N-Heterocyclic Silylenes
Three new stable silylenes, rac-1,3,4-tri-tert-butyl-1,3-diaza-2-silacyclopentane-2-ylide (5), 1,3-di-tert-butyl-4,4-dimethyl-1,3-diaza-2-silacyclopentane-2-ylide (6), and
Insertion Reaction of a Silylene into a N−H Bond of Hydrazine and a [1+4] Cycloaddition with Diphenyl Hydrazone§
The reaction of a stable six-membered N-heterocyclic silylene, LSi (1) [L = CH{(C═CH2)(CMe)(2,6-iPr2C6H3N)2}], with hydrazine and its derivatives is described. 1 reacts with hydrazine to form
Striking reactivity of a stable, zwitterionic silylene towards substituted diazomethanes, azides, and isocyanides.
TLDR
The reactivity of the zwitterionic N-heterocyclic silylene (NHS) LSi is reported, and the silyl cyanide LSi(R)CN (R = cyclohexyl) 4 along with the unexpected azasilacyclobutane 5 (41% yield).
A stable silylene in a reactive environment: Synthesis, reactivity, and silicon extrusion chemistry of a coordinatively unsaturated ruthenium silylene complex containing chloride and η3-P-C-P ligands
Reaction of [(dcypb)ClRu(μ-Cl) 3 Ru(dcypb))(N 2 )] (1) with 4 equiv of the stable silylene 1,3-di-tert-butyl-1,3,2-diazasilol-2-ylidene (SiL N 2 ) yields coordinatively unsaturated RuCl(η 3
Synthesis, structure, and bonding of stable dialkylsilaketenimines.
TLDR
X-ray single-crystal analysis disclosed that molecular structures of 2a and 2b were close to each other and were characterized to be allenic rather than zwitterionic or a silylene-isocyanide complex.
The Thermally Stable Silylene Si[{N(CH2But)}2C6H4-1,2]: Reactivity toward CN Double Bonds
The reaction of the abbreviated as Si(NN)) with the imine Ph2CNSiMe3 gave a 1:1 adduct, the fused bicyclic compound Upon heating, 6 was transformed into the In contrast, treatment of 5 with PhCHNBut
Hydrosilylation of a silicon(II) hydride: synthesis and characterization of a remarkable silylsilylene.
TLDR
The synthesis and characterization of novel monomeric silylsilylenes [(NtBu)(2)C(H)Ph}R] (R=Cl (2), H (4) and compounds 2 and 4 are stable in solution or the solid state, and do not dimerize to form the corresponding disilene.
Evaluation of a silylene divalent lanthanide interaction in the metallocene complex (C5Me5)2Sm[SiNtBuCHCHNtBu]
An R2Si: →Ln(II) complex 1, has been synthesized in 90% yield by reaction of (C5Me5)2Sm with 1,3-di-tert-butyl-2,3-dihydro-1H-1,3,2-diazasilol-2-ylidene in toluene. Structural features of the
...
...