49 research outputs found
The reductive activation of CO2 across a TiâTi double bond: synthetic, structural, and mechanistic studies
[Image: see text] The reactivity of the bis(pentalene)dititanium double-sandwich compound Ti(2)Pn(â )(2) (1) (Pn(â ) = 1,4-{Si(i)Pr(3)}(2)C(8)H(4)) with CO(2) is investigated in detail using spectroscopic, X-ray crystallographic, and computational studies. When the CO(2) reaction is performed at â78 °C, the 1:1 adduct 4 is formed, and low-temperature spectroscopic measurements are consistent with a CO(2) molecule bound symmetrically to the two Ti centers in a ÎŒ:η(2),η(2) binding mode, a structure also indicated by theory. Upon warming to room temperature the coordinated CO(2) is quantitatively reduced over a period of minutes to give the bis(oxo)-bridged dimer 2 and the dicarbonyl complex 3. In situ NMR studies indicated that this decomposition proceeds in a stepwise process via monooxo (5) and monocarbonyl (7) double-sandwich complexes, which have been independently synthesized and structurally characterized. 5 is thermally unstable with respect to a ÎŒ-O dimer in which the TiâTi bond has been cleaved and one pentalene ligand binds in an η(8) fashion to each of the formally Ti(III) centers. The molecular structure of 7 shows a âside-onâ bound carbonyl ligand. Bonding of the double-sandwich species Ti(2)Pn(2) (Pn = C(8)H(6)) to other fragments has been investigated by density functional theory calculations and fragment analysis, providing insight into the CO(2) reaction pathway consistent with the experimentally observed intermediates. A key step in the proposed mechanism is disproportionation of a mono(oxo) di-Ti(III) species to yield di-Ti(II) and di-Ti(IV) products. 1 forms a structurally characterized, thermally stable CS(2) adduct 8 that shows symmetrical binding to the Ti(2) unit and supports the formulation of 4. The reaction of 1 with COS forms a thermally unstable complex 9 that undergoes scission to give mono(ÎŒ-S) mono(CO) species 10. Ph(3)PS is an effective sulfur transfer agent for 1, enabling the synthesis of mono(ÎŒ-S) complex 11 with a double-sandwich structure and bis(ÎŒ-S) dimer 12 in which the TiâTi bond has been cleaved
Pre-organized frustrated Lewis pairs
Geminal frustrated Lewis pairs (FLPs) are expected to exhibit increased reactivity when the donor and acceptor sites are perfectly aligned. This is shown for reactions of the nonfluorinated FLP tBu2PCH2BPh2 with H2, CO2, and isocyanates and supported computationally