56889-90-8Relevant academic research and scientific papers
Carbon Monoxide Cleavage by (silox)3Ta (silox = tBu3SiO(-)): Physical, Theoretical, and Mechanistic Investigations
Neithamer, David R.,LaPointe, Robert E.,Wheeler, Ralph A.,Richeson, Darrin S.,Duyne, Gregory D. Van,Wolczanski, Peter T.
, p. 9056 - 9072 (2007/10/02)
Reduction of (silox)3TaCl2 (1, silox = tBu3SiO(-)) with Na/Hg in THF leads to a three-coordinate, Ta(III) siloxide, (silox)3Ta (2).Derivatization of 2 with excess O2 or H2 provides (silox)3Ta=O (3) and (silox)3TaH2 (4), respectively.At 25 deg C, carbonylation of 2 (0.1-1.0 atm) generates 1/2 3 and 1/42(μ-C2) (5), consistent with a CO uptake of 0.47 equiv.X-ray (P, R = 9.6percent) structural, IR, and Raman studies of dicarbide 5 manifest a near-linear μ-C2 bridge (TaCC = 173 (3) deg), a C=C double bond (1.37 (4) Angstroem, ν(C=C) = 1617 cm-1) and typical TaC double bonds (1.95 (2) Angstroem, ν(Ta=C) = 709 cm-1), respectively.EHMO calculations of a linear μ-C2-bridged D3d 5 indicate that the eg2 HOMO (3A2g, 1Eg, 1A1g) is ca. 80percent Ta (dxz, dyz) and ca. 20percent C (px, py).Magnetic susceptibility measurements of 5 from 2 to 300 K reveal a large temperature-independent susceptibility (25 deg C, μeff = 1.93μB) and a singlet ground state, either 1Eg, 1A1g (D3d) or one arising from a Jahn-Teller distortion of the 1Eg level.Treatment of 2 with CO (ca. 1 atm) at -78 deg C, followed by warming to 25 deg C, results in an uptake of 0.97 equiv. of CO and the production of an inseparable mixture of 3 and a monomeric ketenylidene, (silox)3Ta=C=C=O (6).Diamagnetic 6 (ν(C=O) = 2076 cm-1, 1JCC = 100 Hz), a precursor to 5, is linear according to EHMO calculations.Mechanistic investigations concerning formation of 5 and 6, utilizing labeling experiments, kinetics, and chemical models, support the following sequence of reactions: (1) (silox)3Ta (2) binds CO to form unstable (silox)3TaCO (2-CO). (2) In donor solvents, 2-CO is trapped and stabilized by the solvent (solvent = S) (-78 deg C) as (silox)3STaCO (S-2-CO). (3) Aggregation of S-2-CO and equilibrium amounts of 2-CO, dimerization of 2-CO, disproportionation of monocarbonyl species to (silox)3Ta(CO)2 (2-(CO)2) and 2, which quickly recombine, generates (-78 to -50 deg C) red precipitate n (n, n is probably 2). (4) In nondonor solvents 2-CO either dimerizes or disproportionates to ultimately give n. (5) Degradation of n (ca. 5 deg C), produces ketenylidene (silox)3Ta=C=C=O (6) and oxo (silox)3Ta=O (3). (6) Another (silox)3Ta (2) deoxygenates ketenylidene 6 (ca. 0 deg C), possibly via intermediate (6.2), to afford oxo 3 and a transient vinylidene, (silox)3Ta=C=C: (2-C2), that electronically resembles CO, as substantiated by EHMO arguments. (7) A final (silox)3Ta (2) unit scavenges the vinylidene (2-C2), resulting in 2(μ-C2) (5).Alternatives to the heterogenous dissociative adsorption of CO, the first step in the Fischer-Tropsch process, are suggested on the basis of this work.
Silicon Compounds with Strong Intramolecular Steric Interactions, IX. tert-Butyl Substituted Di- and Trisiloxanes
Weidenbruch, Manfred,Pesel, Helge,Hieu, Dang Van
, p. 31 - 34 (2007/10/02)
The overcrowded molecules 1,1,3,3-tetra-tert-butylsiloxane-1,3-diol (2) and penta-tert-butylsiloxanol (4) have been obtained during the attempted synthesis of tri-tert-butylsilanol and di-tert-butylsilanediol by reaction of tri-tert-butylsilane and di-tert-butylchlorosilane, resp., with silver nitrate.Compounds 2 and 4 were also formed either by condensation of two molecules of di-tert-butylsilanediol or by co-condensation of the silanediol with tri-tert-butylsilanol in the presence of p-toluenesulfonic acid.Reactions of tri-tert-butylsilanol with silicon tetrachloride yielded 1,1,1,5,5,5-hexa-tert-butyl-3,3-dichlorotrisiloxane. - Keywords: 1,1,3,3-Tetra-tert-butylsiloxane-1,3-diol, Penta-tert-butyldisiloxanol, Steric Hindrance, Mass Spectra
