Hydrosilylation of a silicon(II) hydride: synthesis and characterization of a remarkable silylsilylene.

  title={Hydrosilylation of a silicon(II) hydride: synthesis and characterization of a remarkable silylsilylene.},
  author={Shuhua Zhang and Hui-Xian Yeong and Hong-Wei Xi and Kok Hwa. Lim and Cheuk-Wai So},
  volume={16 33},
The synthesis and characterization of novel monomeric silylsilylenes [{PhC(NtBu)(2)}Si--Si{(NtBu)(2)C(H)Ph}R] (R=Cl (2), H (4)) are described. Compound 2 was prepared by the treatment of [{PhC(NtBu)(2)}SiHCl(2)] (1) with two equivalents of potassium graphite, whereas compound 4 was synthesized by the treatment of 1 with four equivalents of potassium graphite. The results suggest that silicon(II) hydride intermediate [{PhC(NtBu)(2)}SiH] was formed in the reduction, which underwent a… 
A silyliumylidene cation stabilized by an amidinate ligand and 4-dimethylaminopyridine.
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.
Reactivity of a silylsilylene bearing a functionalized diaminochlorosilyl substituent.
The results show that the reactions of 2 are initiated by oxidative addition of the divalent silicon center, and then the intermediate formed undergoes a rearrangement involving the diaminochlorosilyl substituent to form compounds 3-8.
Synthesis, Characterization, and Reactivity of an N-Heterocyclic Germanium(II) Hydride: Reversible Hydrogermylation of a Phosphaalkyne
The β-diketiminato germanium(II) chloride complex [(ButMesNacnac)GeCl] (ButMesNacnac = [{N(Mes)C(But)}2CH]−, Mes = mesityl) has been prepared and spectroscopically characterized. Treating this
Bulky Aminotroponiminate-Stabilized Germylene Monochloride and Its Alkyne Derivatives
By means of a two-step synthetic route, aminotroponimine [(t-Bu)2ATI]H (3) with a tert-butyl substituent on the nitrogen atoms has been synthesized from 2-(tosyloxy)tropone. Lithiation of 3 with
Synthesis and characterization of a singlet delocalized 2,4-diimino-1,3-disilacyclobutanediyl and a silylenylsilaimine.
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.
Si=Si Double Bonds: Synthesis of an NHC-Stabilized Disilavinylidene.
An efficient two-step synthesis of the first NHC-stabilized disilavinylidene (Z)-(SIdipp)Si=Si(Br)Tbb (2; SIdipp=C[N(C6H3-2,6-iPr2)CH2]2, Tbb=C6H2-2,6-[CH(SiMe3)2]2-4-tBu, NHC=N-heterocyclic carbene)
Thermal rearrangement of a 1,2-bis(silylene): Synthesis and crystal structure of a silyl-silylene
Abstract Thermal rearrangement of the 1,2-bis(silylene), [{(4-ButPh)C(NDip)2}Si−]2 (Dip = 2,6-diisopropylphenyl, leads to the silyl-silylene, {(4-ButPh)C(NDip)2}Si−Si(H) {N(Dip)C(=NDip)(4-ButPh-H)},
A cyclopentadienyl functionalized silylene – a flexible ligand for Si- and C-coordination†
The synthesis of a 1,2,3,4-tetramethylcyclopentadienyl (Cp4) substituted four-membered N-heterocyclic silylene [{PhC(NtBu)2}Si(C5Me4H)] is reported first. Then, selected reactions with transition
Synthesis and Characterization of an Amidinate-Stabilized Bisgermylene Oxide and Sulfide
The synthesis and characterization of the amidinate-stabilized bisgermylene oxide and sulfide [L2Ge−E−GeL2] (E = O (2), S (3); L2 = ButC(NAr)2, Ar = 2,6-Pri2C6H3) are described. Compound 2 was


A germanium(II) hydride as an effective reagent for hydrogermylation reactions.
The reactivity of the stable germanium(II) hydride LGeH (L = CH{(CMe)(2,6-iPr(2)C(6)H(3)N)}(2)) (2), which contains a low-valent germania atom, is reported on.
Reactivity of a disilylene [{PhC(NBu(t))(2)}Si](2) toward bromine: synthesis and characterization of a stable monomeric bromosilylene.
An X-ray structure of compound 2 has been determined and the result shows that the Si(I)-Si(I) bond in 1 was cleaved by bromine.
Hydrostannylation of ketones and alkynes with LSnH [L = HC(CMeNAr)2, Ar = 2,6-iPr2C6H3].
The reactions of the stable beta-diketiminate tin(II) hydride LSnH and compounds 3, 4, 5, and 7 were characterized by X-ray crystallography, and the resulting structures confirmed the monomeric nature, in which the tin centers reside in a trigonal-pyramidal environment.
Facile Rotation around SiSi Double Bonds in Tetrakis(trialkylsilyl)disilenes
Stable disilenes having two different trialkylsilyl substituents [SiASiBSiSiSiASiB ((E)-2 and (Z)-2) and SiA2SiSiSiB2 (3), where SiA = t-BuMe2Si and SiB = i-Pr2MeSi] were prepared and characterized.
The first stable methyl-substituted disilene: Synthesis, crystal structure, and regiospecific MeLi addition
The reductive debromination of 3,3-dibromo-1,1,5,5-tetra-tert-butyl-2,4-bis(di-tert-butylmethylsilyl)-1,2,4,5-tetramethylpentasilane, [(tBu2MeSi)2MeSi]2SiBr2 (1), gave
Isomeric forms of heavier main group hydrides: experimental and theoretical studies of the [Sn(Ar)H]2 (Ar = terphenyl) system.
Spectroscopic studies show that, in solution, compounds 2, 6, 10, and 14 are predominantly dimeric with Sn-H-Sn bridges, and theoretical calculations showed that increased steric hindrance favors the asymmetric form ArSnSn(H)2Ar relative to the centrosymmetric isomer [ArSn(mu-H)]2 as a result of the widening of the interligand angles at tin.
A remarkable base-stabilized bis(silylene) with a silicon(I)-silicon(I) bond.
The use of an amidinate ligand with tBu substituents on the nitrogen atoms to stabilize heteroleptic silylenes and a Ge dimer is successful, and it seems that such a ligand might also stabilize a Si compound with a Si Si single bond.
High yield access to silylene RSiCl (R = PhC(NtBu)2) and its reactivity toward alkyne: synthesis of stable disilacyclobutene.
A rare example of two five-coordinate silicon centers arranged adjacent to each other in a four-membered ring is reported by the reaction of RSiHCl(2) with bis-trimethyl silyl lithium amide and N-heterocyclic carbene respectively.
Reactions of tin(II) hydride species with unsaturated molecules.
Terphenyl and bdiketiminate ligands have been used for the preparation of substituted tin(II) hydrides and at elevated temperature, SnH2 changed to an insoluble solid of unknown structure.
Synthesis and reactions of a stable 1,2-diaryl-1,2-dibromodisilene: a precursor for substituted disilenes and a 1,2-diaryldisilyne.
The stable diaryldibromodisilene underwent substitution reactions with organometallic reagents on the low-coordinated silicon atom to afford the corresponding substituted disilenes, the characters of which were revealed by spectroscopic and crystallographic analyses.