General principles driving the chemical reactivity of titanium(IV) alkoxides

被引：25

作者：

Biechel, F ^{[1
]}

Dubuc, J ^{[1
]}

Henry, M ^{[1
]}

机构：

[1] Univ Strasbourg, CNRS, UMR 7140, Inst Le Bel,Lab Chim Mol Etat Solide, F-67070 Strasbourg, France

来源：

NEW JOURNAL OF CHEMISTRY | 2004年 / 28卷 / 06期

关键词：

D O I：

10.1039/b312486j

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

The chemical reactivity of titanium(IV) (oxo)alkoxides towards multipodal ligands such as 1,3-propanediol and pentaerythritol is investigated. Two new complexes, [Ti-7(mu(4)-O)(2)(mu(3)-O)(2){O(CH2)(3)O}(mu-OEt)(6)(OEt)(12)] and [Ti-4(mu(2)-OEt)(4)(OEt)(8){mu(4)-(OCH2)(4)C}], have been isolated and characterized using single-crystal X-ray diffraction. The partial charge distribution in these complexes and in previously synthesized ones are described. From these results, it emerges that two general rules govern the chemical reactivity of Ti-IV (oxo) alkoxides. First, bridging OR-groups are systematically more basic than terminal ones and thus should be selectively attacked or substituted by protic XOH reagents. Second, a reduction in coordination is systematically associated with the more electrophilic Ti atoms and thus better solvation of the complexes.

引用

收藏

页码：764 / 769

页数：6

相关论文

共 32 条

[1] XANES AND EXAFS STUDY OF TITANIUM ALKOXIDES [J].

BABONNEAU, F ;

DOEUFF, S ;

LEAUSTIC, A ;

SANCHEZ, C ;

CARTIER, C ;

VERDAGUER, M .

INORGANIC CHEMISTRY, 1988, 27 (18) :3166-3172

[2] MIL-50, an open-framework GaPO with a periodic pattern of small water ponds and dry rubidium atoms:: a combined XRD, NMR, and computational study [J].

Beitone, L ;

Marrot, J ;

Loiseau, T ;

Férey, G ;

Henry, M ;

Huguenard, C ;

Gansmuller, A ;

Taulelle, F .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2003, 125 (07) :1912-1922

[3] Order-disorder in the super-sodalite Zn3Al6(PO4)12, 4tren, 17H2O (MIL-74):: A combined XRD-NMR assessment [J].

Beitone, L ;

Huguenard, C ;

Gansmüller, A ;

Henry, M ;

Taulelle, F ;

Loiseau, T ;

Férey, G .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2003, 125 (30) :9102-9110

[4] Titanium(IV) neopentoxides. X-ray structures of Ti-3(mu(3)-Cl)(mu-OCH2CMe3)(3)(OCH2CMe3)(6) and [Ti(mu-OCH2CMe3)(OCH2CMe3)(3)](2) [J].

Boyle, TJ ;

Alam, TM ;

Mechenbier, ER ;

Scott, BL ;

Ziller, JW .

INORGANIC CHEMISTRY, 1997, 36 (15) :3293-3300

[5] SYNTHESIS AND STRUCTURE OF NOVEL GROUP-IV TRIDENTATE ALKOXIDE COMPLEXES AND CERAMIC THIN-FILMS DERIVED THEREFROM - X-RAY STRUCTURES OF (H3CC(CH2-MU(3)-O)(CH2-MU-O)(2))(2)TI-4(OCH(CH3)(2))(10), (H3CCH2C(CH2-MU-3-O)(CH2-MU-O)(2))(2)TI-4(OCH(CH3)(2))(10), AND (H3CC(CH2-MU-O)(3))(2)ZR-4(MU-OCH(CH3)(2))(2)(OCH(CH3)(2))(8)(1) [J].

BOYLE, TJ ;

SCHWARTZ, RW ;

DOEDENS, RJ ;

ZILLER, JW .

INORGANIC CHEMISTRY, 1995, 34 (05) :1110-1120

[6] SIR88 - A DIRECT-METHODS PROGRAM FOR THE AUTOMATIC SOLUTION OF CRYSTAL-STRUCTURES [J].

BURLA, MC ;

CAMALLI, M ;

CASCARANO, G ;

GIACOVAZZO, C ;

POLIDORI, G ;

SPAGNA, R ;

VITERBO, D .

JOURNAL OF APPLIED CRYSTALLOGRAPHY, 1989, 22 :389-393

[7]

CHEN YW, 1992, MATER RES SOC SYMP P, V271, P57, DOI 10.1557/PROC-271-57

[8]

Clark T. A., 1985, Handbook of Computational Chemistry

[9] SOLUTION STRUCTURE ELUCIDATION OF EARLY-TRANSITION-METAL POLYOXOALKOXIDES USING O-17 NUCLEAR-MAGNETIC-RESONANCE SPECTROSCOPY [J].

DAY, VW ;

EBERSPACHER, TA ;

KLEMPERER, WG ;

PARK, CW ;

ROSENBERG, FS .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1991, 113 (21) :8190-8192

[10] DODECATITANATES - A NEW FAMILY OF STABLE POLYOXOTITANATES [J].

DAY, VW ;

EBERSPACHER, TA ;

KLEMPERER, WG ;

PARK, CW .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1993, 115 (18) :8469-8470

← 1 2 3 4 →