含克劳伊三脚架配体的钛（IV）和锆（IV）的磷酸根、铬酸根和高铼酸根配合物。

Yi Xiao-Yi, Zhang Qian-Feng, Lam Tony C H, Chan Eddie Y Y, Williams Ian D, Leung Wa-Hung

Department of Chemistry, The Hong Kong University of Science and Technology, Clear Water Bay, Kowloon, PR China.

Inorg Chem. 2006 Jan 9;45(1):328-35. doi: 10.1021/ic051329u.

Treatment of titanyl sulfate in dilute sulfuric acid with 1 equiv of NaL(OEt) (L(OEt)(-) = (eta(5)-C(5)H(5))Co{P(O)(OEt)(2)](-)) in the presence of Na(3)PO(4) and Na(4)P(2)O(7) led to isolation of [(L(OEt)Ti)(3)(mu-O)(3)(mu(3-)PO(4))] (1) and [(L(OEt)Ti)(2)(mu-O)(mu-P(2)O(7))] (2), respectively. The structure of 1 consists of a Ti(3)O(3) core capped by a mu(3)-phosphato group. In 2, the P(2)O(7) ligands binds to the two Ti's in a mu:eta(2),eta(2) fashion. Treatment of titanyl sulfate in dilute sulfuric acid with NaL(OEt) and 1.5 equiv of Na(2)Cr(2)O(7) gave [(L(OEt)Ti)(2)(mu-CrO(4))(3)] (3) that contains two L(OEt)Ti(3+) fragments bridged by three mu-CrO(4)(2-)-O,O' ligands. Complex 3 can act as a 6-electron oxidant and oxidize benzyl alcohol to give ca. 3 equiv of benzaldehyde. Treatment of [L(OEt)Ti(OTf)(3)] (OTf(-) = triflate) with [n-Bu(4)N][ReO(4)] afforded [L(OEt)Ti(ReO(4))(2)(mu-O)] (4). Treatment of [L(OEt)MF(3)] (M = Ti and Zr) with 3 equiv of [ReO(3)(OSiMe(3))] afforded [L(OEt)Ti(ReO(4))(3)] (5) and [L(OEt)Zr(ReO(4))(3)(H(2)O)] (6), respectively. Treatment of [L(OEt)MF(3)] with 2 equiv of [ReO(3)(OSiMe(3))] afforded [L(OEt)Ti(ReO(4))(2)F] (7) and [L(OEt)Zr(ReO(4))(2)(mu-F)(2)] (8), respectively, which reacted with Me(3)SiOTf to give [L(OEt)M(ReO(4))(2)(OTf)] (M = Ti (9), Zr (10)). Hydrolysis of [L(OEt)Zr(OTf)(3)] (11) with Na(2)WO(4).xH(2)O and wet CH(2)Cl(2) afforded the hydroxo-bridged complexes [L(OEt)Zr(H(2)O)(mu-OH)(3)(mu(3)-O)]OTf (12) and [L(OEt)Zr(H(2)O)(2)(mu-OH)(2)]OTf (13), respectively. The solid-state structures of 1-3, 6, and 11-13 have been established by X-ray crystallography. The L(OEt)Ti(IV) complexes can catalyze oxidation of methyl p-tolyl sulfide with tert-butyl hydroperoxide. The bimetallic Ti/ Re complexes 5 and 9 were found to be more active catalysts for the sulfide oxidation than other Ti(IV) complexes presumably because Re alkylperoxo species are involved as the reactive intermediates.

在磷酸钠和焦磷酸钠存在的情况下，用1当量的NaL(OEt)（L(OEt)(-) = (η⁵-C₅H₅)Co{P(O)(OEt)₂}₃）处理稀硫酸中的硫酸氧钛，分别得到[(L(OEt)Ti)₃(μ-O)₃(μ₃-PO₄)]（1）和[(L(OEt)Ti)₂(μ-O)(μ-P₂O₇)]（2）。1的结构由一个被μ₃-磷酸根基团封端的Ti₃O₃核心组成。在2中，[P₂O₇]⁴⁻配体以μ:η²,η²的方式与两个钛原子结合。用NaL(OEt)和1.5当量的Na₂Cr₂O₇处理稀硫酸中的硫酸氧钛，得到[(L(OEt)Ti)₂(μ-CrO₄)₃]（3），它包含两个由三个μ-CrO₄²⁻-O,O'配体桥连的L(OEt)Ti³⁺片段。配合物3可以作为一种6电子氧化剂，将苯甲醇氧化生成约3当量的苯甲醛。用[n-Bu₄N][ReO₄]处理[L(OEt)Ti(OTf)₃]（OTf⁻ = 三氟甲磺酸根），得到[[L(OEt)Ti(ReO₄)₂]₂(μ-O)]（4）。用3当量的[ReO₃(OSiMe₃)]处理[L(OEt)MF₃]（M = Ti和Zr），分别得到[L(OEt)Ti(ReO₄)₃]（5）和[L(OEt)Zr(ReO₄)₃(H₂O)]（6）。用2当量的[ReO₃(OSiMe₃)]处理[L(OEt)MF₃]，分别得到[L(OEt)Ti(ReO₄)₂F]（7）和[[L(OEt)Zr(ReO₄)₂]₂(μ-F)₂]（8），它们与Me₃SiOTf反应生成[L(OEt)M(ReO₄)₂(OTf)]（M = Ti（9），Zr（10））。用Na₂WO₄·xH₂O和湿二氯甲烷水解[L(OEt)Zr(OTf)₃]（11），分别得到羟基桥连的配合物[[L(OEt)Zr(H₂O)]₃(μ-OH)₃(μ₃-O)][OTf]₄（12）和[[L(OEt)Zr(H₂O)₂]₂(μ-OH)₂][OTf]₄（13）。1 - 3、6以及11 - 13的固态结构已通过X射线晶体学确定。L(OEt)Ti(IV)配合物可以催化用叔丁基过氧化氢氧化对甲苯硫醚。发现双金属Ti/Re配合物5和9比其他Ti(IV)配合物对硫化物氧化更具活性，可能是因为Re烷基过氧物种作为反应中间体参与其中。