Titanium and niobium complexes stabilized by tris(aminopyridinato) ligands: Evidence of variable denticity in trianionic polydentate ligands

被引：17

作者：

Hillebrand, G ^{[1
]}

Spannenberg, A ^{[1
]}

Arndt, P ^{[1
]}

Kempe, R ^{[1
]}

机构：

[1] UNIV ROSTOCK,IFOK,ABT KOMPLEXKATALYSE,D-18055 ROSTOCK,GERMANY

来源：

ORGANOMETALLICS | 1997年 / 16卷 / 25期

关键词：

D O I：

10.1021/om9704612

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

The reactions of 3 equiv of 4-methyl-2-aminopyridine and 4,6-dimethyl-2-aminopyridine with tris(bromodimethylsilyl)methane in the presence of 3 equiv of triethylamine gave respectively the two tris(aminopyridine) species HC(SiMe2NHC5NH3-4-Me)(3) ((trisAP-4)H-3, 1a) and HC(SiMe2NHC5NH2-4,6-Me-2)(3) ((trisAP-4,6)H-3, 1b). Compound 1a reacted with (Me2N)(3)TiCl via amine elimination to give (trisAP-4)TiCl (2), a mononuclear titanium complex that is coordinated by six nitrogen atoms according to an X-ray analysis. The reaction of NbCl3(DME)(eta(2)-PhC drop CSiMe3) with trilithiated 1b (in situ) formed (trisAP-4,6)Nb(eta(2)-PhC drop CSiMe3) (3). The tris(aminopyridinato) ligand trisAP-4,6 in 3 acts as a pentadentate ligand, in contrast to the hexadentate coordination of trisAP-4 in 2 and 3. NMR investigations of the reaction of 3 with acetylene revealed neither alkyne exchange nor benzene formation.

引用

页码：5585 / 5588

页数：4

共 32 条

[1]

Albright T.A., 1985, ORBITAL INTERACTIONS

[2] TABLES OF BOND LENGTHS DETERMINED BY X-RAY AND NEUTRON-DIFFRACTION .1. BOND LENGTHS IN ORGANIC-COMPOUNDS [J].

ALLEN, FH ;

KENNARD, O ;

WATSON, DG ;

BRAMMER, L ;

ORPEN, AG ;

TAYLOR, R .

JOURNAL OF THE CHEMICAL SOCIETY-PERKIN TRANSACTIONS 2, 1987, (12) :S1-S19

[3]

BAUMANN W, IN PRESS MAGN RESON

[4] DIALKYLAMIDO-TITAN(IV)-CHLORIDE UND ALKOHOLATE [J].

BENZING, E ;

KORNICKER, W .

CHEMISCHE BERICHTE-RECUEIL, 1961, 94 (08) :2263-2267

[5] ALKYNE CYCLIZATIONS AT REDUCED TANTALUM CENTERS - SYNTHESIS AND MOLECULAR-STRUCTURE OF (ETA-6-C6ME6)TA(O-2,6-I-PR2C6H3)2CL [J].

BRUCK, MA ;

COPENHAVER, AS ;

WIGLEY, DE .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1987, 109 (21) :6525-6527

[6] REACTIONS OF NIOBIUM(III) AND TANTALUM(III) COMPOUNDS WITH ACETYLENES .4. POLYMERIZATION OF INTERNAL ACETYLENES [J].

COTTON, FA ;

HALL, WT ;

CANN, KJ ;

KAROL, FJ .

MACROMOLECULES, 1981, 14 (02) :233-236

[7] SYNTHESIS OF VANADIUM AND TITANIUM COMPLEXES OF THE TYPE RM[(ME3SINCH2CH2)3N] (R = CL, ALKYL) AND THE STRUCTURE OF CLV[(ME3SINCH2CH2)3N] [J].

CUMMINS, CC ;

SCHROCK, RR ;

DAVIS, WM .

ORGANOMETALLICS, 1992, 11 (04) :1452-1454

[8] SYNTHESES AND STRUCTURAL STUDIES OF [2-(6-METHYL)PYRIDYL]- AND (8-QUINOLYL)-TRIMETHYLSILYLAMIDO-LITHIUM COMPLEXES [J].

ENGELHARDT, LM ;

JACOBSEN, GE ;

JUNK, PC ;

RASTON, CL ;

SKELTON, BW ;

WHITE, AH .

JOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS, 1988, (04) :1011-1020

[9] VERTICAL 4-ELECTRON-DONOR ALKYNE LIGANDS IN (TRIS(3,5-DIMETHYLPYRAZOLYL)BORATO)NIOBIUM COMPLEXES [J].

ETIENNE, M ;

WHITE, PS ;

TEMPLETON, JL .

ORGANOMETALLICS, 1991, 10 (11) :3801-3803

[10] Tripodal amido-titanium and -zirconium complexes containing a trisilylsilane-derived ligand framework [J].

Findeis, B ;

Schubart, M ;

Gade, LH ;

Moller, F ;

Scowen, I ;

McPartlin, M .

JOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS, 1996, (01) :125-132

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