Synthesis and reactivity of calix[4]arene-supported group 4 imido complexes

被引：76

作者：

Dubberley, SR

Friedrich, A

Willman, DA

Mountford, P

Radius, U

机构：

[1] Univ Karlsruhe, Inst Anorgan Chem, D-76128 Karlsruhe, Germany

[2] Univ Oxford, Inorgan Chem Lab, Oxford OX1 3QR, England

来源：

CHEMISTRY-A EUROPEAN JOURNAL | 2003年 / 9卷 / 15期

关键词：

calixarenes; coordination modes; imido ligands; titanium; zirconium;

D O I：

10.1002/chem.200204656

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

New mononuclear titanium and zirconium imido complexes [M(NR)(R'(2)calix)] [M=Ti, R'=Me, R=tBu (1), R = 2,6-C6H3Me2 (2), R= 2,6-C(6)H(3)iPr(2) (3), R = 2,4,6-C6H2Me3 (4); M = Ti, R'= Bz, R = tBu (5), R = 2,6C(6)H(3)iPr(2) (6), R = 2,6-C6H3iPr2 (7); M = Zr, R'= Me, R = 2,6-C(6)H(3)iPr(2) (8)] supported by 1,3-diorganyl ether p-tert-butylcalix[4]arenes (R'2calix) were prepared in good yield from the readily available complexes [MCl2(Me(2)calix)], [Ti(NR)Cl-2(PY)(3)], and [Ti(NR)Cl-2(NHMe2)(2)]. - The crystallographically characterised complex [Ti(NtBu)(Me(2)c-alix)] (1) reacts readily with CO2, CS2, and p-tolyl-isocyanate to give the isolated complexes [Ti{N(tBu)C(O)(Me(2)calix)] (10), [ji(mu-O)(Me(2)calix)}(2})1 (11), [Ti(mu-S)(Me(2)calix)] (12), and [Ti(N(tBu)C(O)N(-4-C6H4Me))(Me2calix)] (13). In the case of CO2 and CS2, the addition of the heterocumulene to the Ti-N multiple bond is followed by a cycloreversion reaction to give the dinuclear complexes 11 and 12. The X-ray structure of 13.4 . (C7H8) clearly establishes the N,N'-coordination mode of the ureate ligand in this compound. Com-

引用

页码：3634 / 3654

页数：21

共 78 条

[1] Evaluation of the relative importance of Ti-Cl•••H-N hydrogen bonds and supramolecular interactions between perfluorophenyl rings in the crystal structures of [Ti(NR)Cl2(NHMe2)2] (R = iPr, C6H5 or C6F5) [J].