RESUMO
We report a combined experimental and computational study of the synthesis and electronic structure of titanium borylimido compounds. Three new synthetic routes to this hitherto almost unknown class of Group 4 imide are presented. The double-deprotonation reaction of the borylamine H2NB(NAr'CH)2 (Ar' = 2,6-C6H3iPr2) with Ti(NMe2)2Cl2 gave Ti{NB(NAr'CH)2}Cl2(NHMe2)2, which was easily converted to Ti{NB(NAr'CH)2}Cl2(py)3. This compound is an entry point to other borylimides, for example, reacting with Li2N2pyrNMe to form Ti(N2pyrNMe){NB(NAr'CH)2}(py)2 and with 2 equiv of NaCp to give Cp2Ti{NB(NAr'CH)2}(py) (23). Borylamine-tert-butylimide exchange between H2NB(NAr'CH)2 and Cp*Ti(NtBu)Cl(py) under forcing conditions afforded Cp*Ti{NB(NAr'CH)2}Cl(py), which could be further substituted with guanidinate or pyrrolide-amine ligands to give Cp*Ti(hpp){NB(NAr'CH)2} (16) and Cp*Ti(NpyrNMe2){NB(NAr'CH)2} (17). The Ti-Nim distances in compounds with the NB(NAr'CH)2 ligand were comparable to those of the corresponding arylimides. Dialkyl- or diaryl-substituted borylamines do not undergo the analogous double-deprotonation or imide-amine exchange reactions. Reaction of (Cpâ³2Ti)2(µ2:η1,η1-N2) with N3BMes2 gave the base-free, diarylborylimide Cpâ³2Ti(NBMes2) (26) by an oxidative route; this compound has a relatively long Ti-Nim bond and large Cpâ³-Ti-Cpâ³ angle. Reaction of 16 with H2NtBu formed equilibrium mixtures with H2NB(NAr'CH)2 and Cp*Ti(hpp)(NtBu) (ΔrG = -1.0 kcal mol-1). In contrast, the dialkylborylimide Cp*Ti{MeC(NiPr)2}(NBC8H14) (2) reacted quantitatively with H2NtBu to give the corresponding tert-butylimide and borylamine. The electronic structures and imide-amine exchange reactions of half-sandwich and sandwich titanium borylimides have been evaluated using density functional theory (DFT), supported by quantum theory of atoms in molecules (QTAIM) and natural bond orbital (NBO) analysis, and placed more generally in context with the well-established alkyl- and arylimides and hydrazides. The calculations find that Ti-Nim bonds for borylimides are stronger and more covalent than in their organoimido or hydrazido analogues, and are strongest for alkyl- and arylborylimides. Borylamine-tert-butylimide exchange reactions fail for H2NBR2 (R = hydrocarbyl) but not for H2NB(NAr'CH)2 because the increased strength of the new Ti-Nim bond for the former is outweighed by the increased net H-N bond strengths in the borylamine. Variation of the Ti-Nim bond length over short distances is dominated by π-interactions with any appropriate orbital on the Nim atom organic substituent. However, over the full range of imides and hydrazides studied, overall bond energies do not correlate with bond length but with the Ti-Nim σ-bond character and the orthogonal π-interaction.
RESUMO
Reaction of Ti(N2(iPr)N)(NNPh2)(py) with Ph(R)SiH2 (R = H, Ph) or 9-BBN gave reductive cleavage of the N(α)-N(ß) bond and formation of new silyl- or boryl-amido ligands. The corresponding reactions of Cp*Ti{MeC(N(i)Pr)2}(NNR2) (R = Me or Ph) with HBPin or 9-BBN gave borylhydrazido-hydride or borylimido products, respectively. N(α) and N(ß) atom transfer and dehydrogenative coupling reactions are also reported.
RESUMO
Glycerol is converted to a mixture of butyric and isobutyric acid by rhodium- or iridium-catalysed carbonylation using HI as the co-catalyst. The initial reaction of glycerol with HI results in several intermediates that lead to isopropyl iodide, which upon carbonylation forms butyric and isobutyric acid. At low HI concentration, the intermediate allyl iodide undergoes carbonylation to give vinyl acetic acid and crotonic acid. Higher polyols C(n)H(n+2)(OH)(n) are carbonylated to the corresponding C(n+1) mono-carboxylic acids.