2 research outputs found
Synthesis and Reactivity of Titanium Hydrazido Complexes Supported by Diamido-Ether Ligands
No full textThe synthesis and reactivity of titanium
diphenyl hydrazido(2−) complexes supported by the diamido-ether
ligands OÂ(2-C<sub>6</sub>H<sub>4</sub>NSiMe<sub>3</sub>)<sub>2</sub> (N<sub>2</sub><sup>Ar</sup>O) and OÂ(CH<sub>2</sub>CH<sub>2</sub>NSiMe<sub>3</sub>)<sub>2</sub> (N<sub>2</sub>O) are described. Reaction
of Li<sub>2</sub>N<sub>2</sub><sup>Ar</sup>O or Li<sub>2</sub>N<sub>2</sub>O with TiÂ(NNPh<sub>2</sub>)ÂCl<sub>2</sub>(py)<sub>3</sub> afforded
TiÂ(N<sub>2</sub><sup>Ar</sup>O)Â(NNPh<sub>2</sub>)Â(py)<sub>2</sub> (<b>14</b>) or TiÂ(N<sub>2</sub>O)Â(NNPh<sub>2</sub>)Â(py)<sub>2</sub> (<b>15</b>) with κ<sup>3</sup>-<i>mer</i>-bound
diamido-ether ligands. Reaction with <sup>t</sup>Bu-bipy (4,4′-di-<i>tert</i>-butyl-2,2′-bipyridyl) or bipy (2,2′-bipyridyl)
gave a switch to κ<sup>3</sup>-<i>fac</i>-coordination.
Reaction of <b>15</b> with Ar′NCO (Ar′ = 2,6-C<sub>6</sub>H<sub>3</sub><sup>i</sup>Pr<sub>2</sub>) gave TiÂ{OÂ(CH<sub>2</sub>CH<sub>2</sub>NSiMe<sub>3</sub>)Â(CH<sub>2</sub>CH<sub>2</sub>NCÂ(O)ÂNÂ(SiMe<sub>3</sub>)ÂAr′)}-{NÂ(NPh<sub>2</sub>)ÂCÂ(O)ÂNÂ(Ar′)},
in which the substrate has inserted into a Ti–N<sub>amide</sub> bond of N<sub>2</sub>O as well as adding to the TiN<sub>α</sub> multiple bond. With Ar′NCS the [2+2] cycloaddition
product TiÂ(N<sub>2</sub>O)Â{NÂ(NPh<sub>2</sub>)ÂCÂ(NAr′)ÂS}Â(py)
was obtained, and with Ar′NCSe a mixture was formed including
Ti<sub>2</sub>(N<sub>2</sub>O)<sub>2</sub>(μ-Se)<sub>2</sub>. Both <b>14</b> and <b>15</b> reacted with Ar<sup>Fx</sup>CN (Ar<sup>Fx</sup> = C<sub>6</sub>H<sub>3</sub>F<sub>2</sub> or
C<sub>6</sub>F<sub>5</sub>) to give TiN<sub>α</sub> bond
insertion products of the type TiÂ(L)Â{NCÂ(Ar<sup>Fx</sup>)ÂNNPh<sub>2</sub>}Â(py)<sub>2</sub> (L = N<sub>2</sub><sup>Ar</sup>O or N<sub>2</sub>O) containing hydrazonamide ligands. Reaction of <b>14</b> with
XylNC (Xyl = 2,6-C<sub>6</sub>H<sub>3</sub>Me<sub>2</sub>) gave only
the isonitrile σ-adduct TiÂ(N<sub>2</sub><sup>Ar</sup>O)Â(NNPh<sub>2</sub>)Â(py)Â(CNXyl), whereas <b>15</b> underwent N<sub>α</sub>–N<sub>β</sub> bond reductive cleavage with <sup>t</sup>BuNC or XylNC forming TiÂ(N<sub>2</sub>O)Â(NPh<sub>2</sub>)Â(NCN<sup>t</sup>Bu) or TiÂ{OÂ(CH<sub>2</sub>CH<sub>2</sub>NSiMe<sub>3</sub>)Â(CH<sub>2</sub>CH<sub>2</sub>NCNÂ(SiMe<sub>3</sub>)ÂXyl)}Â(NPh<sub>2</sub>)Â(NCNXyl) (<b>27</b>). Both contain metalated carbodiimide
ligands, but in <b>27</b> an additional reaction of XylNC with
the Ti–N<sub>amide</sub> bond of N<sub>2</sub>O has taken place.
Compound <b>15</b> also reacted with a number of internal alkynes
RCCR′ (R = R′ = Me or Ph; R = Me, R′ = aryl)
to give N<sub>α</sub>–N<sub>β</sub> bond reductive
cleavage products of the type TiÂ{OÂ(CH<sub>2</sub>CH<sub>2</sub>NSiMe<sub>3</sub>)Â(CH<sub>2</sub>CH<sub>2</sub>NCÂ(R)ÂCÂ(R′)ÂNSiMe<sub>3</sub>}Â(NPh<sub>2</sub>), again involving a reaction of a Ti–N<sub>amide</sub> bond
MOESM1 of Hydrocarbon bio-jet fuel from bioconversion of poplar biomass: techno-economic assessment
No full textAdditional file 1. Temperature and pressure of major unit operations from Aspen modeling, and the capital scaling factor
