Taking TiF4 complexes to extremes--the first examples with phosphine co-ligands.
Taking TiF4 complexes to extremes--the first examples with phosphine co-ligands.
复制标题
将 TiF4 配合物发挥到极致——第一个使用膦辅助配体的例子。
作者：
M. Jura;W. Levason;Edmund Petts;G. Reid;M. Webster;Wenjian Zhang
由[TIF(4)(MeCN)(2)]和严格无水CH(2)Cl(2)中的双膦[TIF(4)(双膦)](双膦=o-C(6)H(4)(PME(2))(2)，R(2)P(CH(2))(2)PR(2)，R=Me或Et)合成了TIF(4)，[TIF(4)(双膦)](双膦=o-C(6)H(4)(PME(2))(2)，R(2)P(CH(2))(2)，R=Me或Et)。红外光谱和紫外可见光谱。测定了[TIF(4){Et(2)P(CH(2))(2)Pet(2)}]的晶体结构，晶体结构为扭曲的六配位几何构型，具有不同的Ti-F(TRAF)和Ti-F(TRANSP)间距和长的Ti-P键。较弱的软施主配体包括Ph(3)P，Ph(2)P(CH(2))(2)PPh(2)，o-C(6)H(4)(PPh(2))(2)，Ph(2)As(CH(2))(2)ASPh(2)，o-C(6)H(4)(ASME(2))(2)和(I)PrS(CH(2))(2)S(I)Pr不与TIF(4)形成稳定的络合物，尽管令人惊讶的是，以前未知的双质子化配体阳离子[Lh(2)][Ti(4)F(18)](L=o-C(6)H(4)(PPh(2))(2)，o-C(6)H(4)(ASME(2))(2)和(I)Pr(CH(2))(2)S(I)Pr)的氟代(IV)盐在某些情况下形成为少量副产物。[o-C(6)H(4)(PPh(2)H)(2)][Ti(4)F(18)]的结构展示了第一个二质子化邻苯二膦的结构。报道了一系列TIF(4)与硬N或O-给体配体的加合物的合成和全光谱表征，以及晶体结构[TIF(4)(THF)(2)]、[TIF(4)(Ph(3)EO)(2)]·2CH(2)Cl(2)(E=P或As)和[TIF(4)(Bipy)]。
The first soft donor adducts of TiF(4), [TiF(4)(diphosphine)] (diphosphine = o-C(6)H(4)(PMe(2))(2), R(2)P(CH(2))(2)PR(2), R = Me or Et) have been prepared from [TiF(4)(MeCN)(2)] and the diphosphines in rigorously anhydrous CH(2)Cl(2), as extremely moisture sensitive yellow solids, and characterised by multinuclear NMR ((1)H, (31)P, (19)F), IR and UV/vis spectroscopy. The crystal structure of [TiF(4){Et(2)P(CH(2))(2)PEt(2)}] has been determined and shows a distorted six-coordinate geometry with disparate Ti-F(transF) and Ti-F(transP) distances and long Ti-P bonds. Weaker soft donor ligands including Ph(3)P, Ph(2)P(CH(2))(2)PPh(2), o-C(6)H(4)(PPh(2))(2), Ph(2)As(CH(2))(2)AsPh(2), o-C(6)H(4)(AsMe(2))(2) and (i)PrS(CH(2))(2)S(i)Pr do not form stable complexes with TiF(4), although surprisingly, fluorotitanate(IV) salts of the previously unknown doubly protonated ligand cations [LH(2)][Ti(4)F(18)] (L = o-C(6)H(4)(PPh(2))(2), o-C(6)H(4)(AsMe(2))(2) and (i)PrS(CH(2))(2)S(i)Pr) are formed in some cases as minor by-products. The structure of [o-C(6)H(4)(PPh(2)H)(2)][Ti(4)F(18)] shows the first authenticated example of a diprotonated o-phenylene-diphosphine. The synthesis and full spectroscopic characterisation are reported for a range of TiF(4) adducts with hard N- or O-donor ligands for comparison purposes, along with crystal structures of [TiF(4)(thf)(2)], [TiF(4)(Ph(3)EO)(2)]·2CH(2)Cl(2) (E = P or As), and [TiF(4)(bipy)].