Toward the Understanding of Radical Reactions: Experimental and Computational Studies of Titanium(III) Diamine Bis(phenolate) Complexes
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资源简介：
Radical
reactions of titanium(III) [Ti(tBu2O2NN′)Cl(S)] (S = THF, 1; S = py, 2; tBu2O2NN′
= Me2N(CH2)2N(CH2-2-O-3,5-tBu2C6H2)2) are described. Reactions with neutral electron acceptors
led to metal oxidation to Ti(IV), [Ti(tBu2O2NN′)Cl(TEMPO)] (4) being formed
with the TEMPO radical and [Ti(tBu2O2NN′)Cl2] (9) with PhNNPh.
[Ti(tBu2O2NN′)Cl2] was also formed when [Ti(tBu2O2NN′)Cl(S)] was oxidized by [Cp2Fe][BPh4], but the [Cp2Fe][PF6] analogue yielded
[Ti(tBu2O2NN′)ClF] (8). The reactions of [Ti(tBu2O2NN′)Cl(S)] with O2 gave [Ti(tBu2O2NN′)Cl]2(μ-O)
(3). The DFT calculated Gibbs energy for the above reaction
showed it to be exergonic (ΔG298 = −123.6
kcal·mol–1). [Ti(tBu2O2NN′)(CH2Ph)(S)] (S = THF, 5; py, 6) are not stable in solution for long periods
and in diethyl ether gave 1:1 cocrystals of [Ti(tBu2O2NN′)(CH2Ph)2]
(7) and [Ti(tBu2O2NN′)Cl]2(μ-O) (3), most probably
resulting from a disproportionation process of titanium(III) followed
by oxygen abstraction by the resulting Ti(II) species. The oxidation
of [Ti(tBu2O2NN′)(κ2-{CH2-2-(NMe2)-C6H4})] (10), which is a Ti(III) benzyl stabilized by the
intramolecular coordination of the NMe2 moiety, led to
a complex mixture. Recrystallization of this mixture under air led
to a 1:1 cocrystal of two coordination isomers of the titanium oxo
dimer (3). In one of these isomers, one metal is pentacoordinate
and the dimethylamine moiety of the diamine bis(phenolate) ligand
is not bonded to the metal, displaying a coordination mode of the
ligand never observed before. The other titanium center is distorted
octahedral with two cis-phenolate moieties. In the
second unit, the coordination of the two ancillary ligands to the
titanium centers reveals mutually cis-phenolate groups
in one-half of the molecule and trans-coordinated
in the other titanium center, keeping a distorted octahedral environment
around each titanium.
创建时间：
2016-02-19
