Reactivity of boranes with a titanium(IV) amine tris(phenolate) alkoxide complex; formation of a Ti(IV) tetrahydroborate complex, a Ti(III) dimer and a Ti(IV) hydroxide Lewis acid adduct

被引:17
作者
Johnson, Andrew L. [1 ]
Davidson, Matthew G. [1 ]
Mahon, Mary F. [1 ]
机构
[1] Univ Bath, Dept Chem, Bath BA2 7AY, Avon, England
关键词
D O I
10.1039/b708378e
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
Treatment of the titanium(IV) alkoxide complex [Ti((OPr)-Pr-i)(OC6Me2H2CH2)(3)N] (2) with BH3 center dot THF, as part of a study into the utility and reactivity of (2) in the metal mediated borane reduction of acetophenone, results in alkoxide-hydride exchange and formation of the structurally characterised titanium(IV) tetrahydroborate complex [Ti{BH4}(OC6Me2H2CH2)(3)N] (3). Complex (3) readily undergoes reduction to form the isolable titanium(III) species [Ti(OC6Me2H2CH2)(3)N](2) (4). Reaction of (2) with B(C6F5)(3) results in formation of the Lewis acid adduct [Ti(OC6Me2H2CH2)(3)N][HO center dot B(C6F5)(3)] (5). In comparison, treatment of the less sterically encumbered alkoxide Ti((OPr)-Pr-i)(4) with B(C6F5)(3) results in alkoxide-aryl exchange and formation of the organometallic titanium complex [Ti((OPr)-Pr-i)(3)(C6F5)](2) (6). The molecular structures of 3, 4, 5 and 6 have been determined by X-ray diffraction.
引用
收藏
页码:5405 / 5411
页数:7
相关论文
共 57 条
[11]   Reactivity of [CP2Ti(CO)2] towards nitrile and water adducts of B(C6F5)3:: Formation of [CP2Ti(η2-F3CC6H4CN)•B(C6F5)3] and [Cp2Ti][HOB(C6F5)3] with a Ti•••F interaction [J].
Choukroun, R ;
Lorber, C ;
Vendier, L .
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, 2004, (02) :317-321
[12]   Reactivity of [Cp2Ti(CO)2] and B(C6F5)3:: Formation of the acylborane complexes [Cp2Ti(CO)(η2-OCB(C6F5)3)] and [Cp2Ti(THF)(η2-OCB(C6F5)3)] [J].
Choukroun, R ;
Lorber, C ;
Lepetit, C ;
Donnadieu, B .
ORGANOMETALLICS, 2003, 22 (10) :1995-1997
[13]   Reactions of oxo- and peroxo-molybdenum complexes with B(C6F5)3:: crystal structures of cis-[MoO{OB(C6F5)3}(η2-ONEt2)2] and cis-[MoO{OB(C6F5)3}{η2-PhN(O)C(O)Ph}2] [J].
Doerrer, LH ;
Galsworthy, JR ;
Green, MLH ;
Leech, MA ;
Muller, M .
JOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS, 1998, (19) :3191-3194
[14]   Tris(pentafluorophenyl)borane: a special boron Lewis acid for special reactions [J].
Erker, G .
DALTON TRANSACTIONS, 2005, (11) :1883-1890
[15]   Systematic metallaborane chemistry [J].
Fehlner, TP .
ORGANOMETALLICS, 2000, 19 (14) :2643-2651
[16]  
FEHLNER TP, CONT BORON CHEM
[17]   Complexes of tris(pentafluorophenyl)boron with nitrogen-containing compounds: Synthesis, reactivity and metallocene activation [J].
Focante, F ;
Mercandelli, P ;
Sironi, A ;
Resconi, L .
COORDINATION CHEMISTRY REVIEWS, 2006, 250 (1-2) :170-188
[18]   Reactions of transition-metal oxo complexes with B(C6F5)3: Crystal structures of [V{OB(C6P5)(3)}(acac)(2)], [Ti{OB(C6F5)(3)}(acac)(2)] and cis-[MoO{OB(C6F5)(3)}(acac)(2)] (acac equals acetylacetonate) [J].
Galsworthy, JR ;
Green, MLH ;
Muller, M ;
Prout, K .
JOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS, 1997, (08) :1309-1313
[19]   Titanium and zirconium complexes of dianionic and trianionic amine - Phenolate-type ligands in catalysis of lactide polymerization [J].
Gendler, Shimrit ;
Segal, Sharon ;
Goldberg, Israel ;
Goldschmidt, Zeev ;
Kol, Moshe .
INORGANIC CHEMISTRY, 2006, 45 (12) :4783-4790
[20]   CHIRAL TITANIUM ALKOXIDES AS CATALYSTS FOR THE ENANTIOSELECTIVE REDUCTION OF KETONES WITH BORANES [J].
GIFFELS, G ;
DREISBACH, C ;
KRAGL, U ;
WEIGERDING, M ;
WALDMANN, H ;
WANDREY, C .
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 1995, 34 (18) :2005-2006