含 Kläui 三角架配体 [(eta5-C5H5)Co{P(O)(OEt)2}3]−的杂核 Ti(IV)-Ru(II) 和 Ti(IV)-Re(I) 硫酸盐配合物。

Heterometallic Ti(IV)-Ru(II) and Ti(IV)-Re(I) sulfato complexes containing the Kläui tripodal ligand [(eta5-C5H5)Co{P(O)(OEt)2}3]-.

机构信息

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

出版信息

Dalton Trans. 2010 Jun 28;39(24):5737-41. doi: 10.1039/c001604g. Epub 2010 May 24.

DOI:10.1039/c001604g

PMID:20498897

Abstract

Treatment of [(L(OEt))(2)Ti(2)(mu-O)(2)(mu-SO(4))] (L(OEt)(-) = (eta(5)-C(5)H(5))Co{P(O)(OEt)(2)}(3)) with [Ru(H)(Cl)(CO)(PPh(3))(3)] and Ag(OTf) (OTf(-) = triflate) in the presence of Na(2)CO(3) gave the Ti(IV)-Ru(II) complex [(L(OEt))(2)Ti(2)(mu-O)(3)(mu(3)-SO(4))Ru(CO)(PPh(3))(2)] (2) whereas that with [Re(CO)(5)(OTf)] afforded the Ti(IV)-Re(I) complex [H(L(OEt))(2)Ti(2)(mu-O)(3)(mu-SO(4))Re(CO)(3)(H(2)O)] (3). The crystal structures of complexes 2.HOTf and 3.2/3(Et(3)NHOTf).5/12(H(2)O) have been determined. Complex 2 consists of an adamantane-like Ti(2)RuSO(6) core, in which the {Ru(II)(PPh(3))(2)(CO)} moiety is facially coordinated to a tridentate-O,O',O''(sulfate) (L(OEt))(2)Ti(2)(mu-O)(3)(mu(3)-SO(4)) metalloligand. The anion (L(OEt))(2)Ti(2)(mu-O)(3)(mu-SO(4))Re(CO)(3)(H(2)O) in 3 can be viewed as consisting of a fac-{Re(I)(CO)(3)} fragment coordinated with one aqua ligand and a bidentate-O,O'-(L(OEt))(2)Ti(2)(mu-O)(3)(mu-SO(4)) metalloligand.

摘要

[(L(OEt))(2)Ti(2)(μ-O)(2)(μ-SO(4))]（L(OEt)(-) = (eta(5)-C(5)H(5))Co{P(O)(OEt)(2)}(3)) 与 [Ru(H)(Cl)(CO)(PPh(3))(3)] 和 Ag(OTf)（OTf(-) = 三氟甲磺酸根）在 Na(2)CO(3)的存在下反应，得到 Ti(IV)-Ru(II) 配合物 [(L(OEt))(2)Ti(2)(μ-O)(3)(μ(3)-SO(4))Ru(CO)(PPh(3))(2)]（2），而与 [Re(CO)(5)(OTf)] 反应则得到 Ti(IV)-Re(I) 配合物 [H(L(OEt))(2)Ti(2)(μ-O)(3)(μ-SO(4))Re(CO)(3)(H(2)O)]（3）。配合物 2.HOTf 和 3.2/3(Et(3)NHOTf).5/12(H(2)O) 的晶体结构已被确定。配合物 2 由一个金刚烷样的 Ti(2)RuSO(6) 核组成，其中 {Ru(II)(PPh(3))(2)(CO)} 部分是 fac-配位的，与一个三齿-O,O',O''(硫酸盐) (L(OEt))(2)Ti(2)(μ-O)(3)(μ(3)-SO(4)) 金属配体配位。阴离子 (L(OEt))(2)Ti(2)(μ-O)(3)(μ-SO(4))Re(CO)(3)(H(2)O) 在 3 中可以看作是由一个 fac-{Re(I)(CO)(3)} 片段与一个水分子配位，与一个双齿-O,O'-(L(OEt))(2)Ti(2)(μ-O)(3)(μ-SO(4)) 金属配体配位。