- A vinyl silylsilylene and its activation of strong homo- and heteroatomic bonds
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The facile synthesis of a rare two-coordinate acyclic silylene (R2Si:) that is stabilized using a bulky vinylic N-heterocyclic olefin ligand and the strongly σ-donating hypersilyl group [Si(SiMe3)3]- is reported. This vinyl-substituted silylene exhibits an excellent combination of prolonged thermal stability along with high reactivity towards small molecules. Despite being stable for months in solution, the reactivity of this new silylene is manifest in its ambient temperature activation of strong B-H, Si-Cl, C-O, P-P and C-H bonds.
- Roy, Matthew M. D.,Ferguson, Michael J.,McDonald, Robert,Zhou, Yuqiao,Rivard, Eric
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p. 6476 - 6481
(2019/07/12)
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- Deposition of metal films based upon complementary reactions
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A method comprises contacting a compound having formulae (1) with a compound having formula MLo to form a metal: [in-line-formulae][M(SiR3)m(L1)p]n??(1)[/in-line-formulae] wherein M is Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Al, a second row transition metal or a third row transition metal;R are each independently H, C1-C6 alkyl or —Si(R″)3;R″ are each independently H or C1-C6 alkyl;m is an integer from 1 to 3;n is a number representing the formation of aggregates or polymeric material;L1 is a neutral donor ligand; L is a ligand; p is an integer from 0 to 6; and o is an integer representing the number of ligands bonded to MLo.
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Page/Page column 17
(2017/01/31)
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- Reductive elimination of hypersilyl halides from zinc(II) complexes. implications for electropositive metal thin film growth
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Treatment of Zn(Si(SiMe3)3)2 with ZnX2 (X = Cl, Br, I) in tetrahydrofuran (THF) at 23 °C afforded [Zn(Si(SiMe3)3)X(THF)]2 in 83-99% yield. X-ray crystal structures revealed dimeric structures with Zn2X2 cores. Thermogravimetric analyses of [Zn(Si(SiMe3)3)X(THF)]2 demonstrated a loss of coordinated THF between 50 and 155°C and then single-step weight losses between 200 and 275°C. The nonvolatile residue was zinc metal in all cases. Bulk thermolyses of [Zn(Si(SiMe3)3)X(THF)]2 between 210 and 250°C afforded zinc metal in 97-99% yield, Si(SiMe3)3X in 91-94% yield, and THF in 81-98% yield. Density functional theory calculations confirmed that zinc formation becomes energetically favorable upon THF loss. Similar reactions are likely to be general for M(SiR3)n/MXn pairs and may lead to new metal-film-growth processes for chemical vapor deposition and atomic layer deposition.
- Sirimanne, Chatu T.,Kerrigan, Marissa M.,Martin, Philip D.,Kanjolia, Ravindra K.,Elliott, Simon D.,Winter, Charles H.
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supporting information
p. 7 - 9
(2015/03/03)
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- The nucleophilic silyl radical: Dual-Parameter correlation analysis of the relative rates of bromine-atom abstraction reactions as measured by a rigorous methodology
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The relative rates [k(R)(Y) values] of bromine-atom abstraction reactions of 13 p-Y-substituted benzyl bromides (1Y's : Y = H, Et, tBu, Me3Si, MeS, Ph, P, Cl, Br, CF3, CN, CO2Me,SO2Me) by tris(trimethylsilyl) silyl radicals [(Me3Si)3Si.] in cyclohexane at 80°C have been measured by a rigorous methodology. Correlation analysis of the kinetic data by the dual-parameter equation (log k(H)/k(H) = ρ(x)σ(x)+ρ.σ.) shows that the silyl radical is distinctly nucleophilic and the transition states of the bromine-atom abstraction reactions are affected by both the polar and spindelocalization effects of the Y-substituents. Comparison of the |ρ(p) / ρ(jj).| values suggests that the contribution of the spin-delocalization effects in this Br-atom abstraction reaction may be greater than the spin-delocalization effects in some H-atom abstraction reactions.
- Jiang, Xi-Kui,Ding, William Fa-Xiang,Zhang, Yu-Huang
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p. 8479 - 8490
(2007/10/03)
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