Molecular structure of 2,2'-thiobis(4-methyl-6-tert-butylphenoxy) titanium diisopropoxy. Influence of titanium-sulfur interaction on coordination geometry

被引:82
作者
Porri, L [1 ]
Ripa, A [1 ]
Colombo, P [1 ]
Miano, E [1 ]
Capelli, S [1 ]
Meille, SV [1 ]
机构
[1] POLITECN MILAN,DIPARTIMENTO CHIM,I-20133 MILAN,ITALY
关键词
titanium; 2,2'-thiobisphenoxy ligand; sulfur; sulfide; X-ray structure; Ti-S interaction;
D O I
10.1016/0022-328X(95)06021-N
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
The molecular structure of 2,2'-thiobis(4-methyl-6-tert-butylphenoxy) titanium diisopropoxy (la) has been determined, The molecule exists as a dimer, in which the 1,3-dioxadititanacycle is supported by two bridging (i)Pro ligands. The coordination environment about each Ti center is best described as a distorted octahedron, where the S atom and one (i)Pro ligand occupy the axial positions, whilst two terminal phenolate and two bridging (i)Pro ligands occupy the equatorial sites, The eight-membered dioxatitanacycle adopts a symmetric-syn boat conformation, which allows for a significant sulfur-titanium interaction (S-Ti distance 2.724(2) Angstrom). A comparison between these structural features and those reported for the monomeric tetrahedral complexes 2b and 2d, where the sulfur atom is replaced by a methylene bridge in the bisphenoxy ligand, highlights the influence of the S-Ti interaction on coordination geometry, The structural features suggested for 1a to account for the higher catalytic activity of 1a/MAO in polymerization of alpha-olefins as compared with 2a/MAo are clearly demonstrated.
引用
收藏
页码:213 / 217
页数:5
相关论文
共 38 条
[1]   COMPLETION AND REFINEMENT OF CRYSTAL-STRUCTURES WITH SIR92 [J].
ALTOMARE, A ;
CASCARANO, G ;
GIACOVAZZO, C ;
GUAGLIARDI, A .
JOURNAL OF APPLIED CRYSTALLOGRAPHY, 1993, 26 (pt 3) :343-350
[2]  
[Anonymous], 1992, INT TABLES CRYSTALLO, VC
[3]   SYNTHETIC, STRUCTURAL, AND PHYSICAL STUDIES OF TITANIUM COMPLEXES OF CATECHOL AND 3,5-DI-TERT-BUTYLCATECHOL [J].
BORGIAS, BA ;
COOPER, SR ;
KOH, YB ;
RAYMOND, KN .
INORGANIC CHEMISTRY, 1984, 23 (08) :1009-1016
[4]  
BOTT SG, 1986, J CHEM SOC CHEM COMM, V315, pC9
[5]   STRUCTURALLY WELL CHARACTERIZED BINAPHTHOLATE TITANIUM CHLORIDE LEWIS-ACIDS - EVIDENCE FOR ACTIVE DINUCLEAR CATALYSTS IN A DIELS-ALDER PROCESS [J].
BOYLE, TJ ;
EILERTS, NW ;
HEPPERT, JA ;
TAKUSAGAWA, F .
ORGANOMETALLICS, 1994, 13 (06) :2218-2229
[6]   KINETICS AND THERMODYNAMICS OF INTRAMOLECULAR AND INTERMOLECULAR REARRANGEMENT IN BINAPHTHOLATE COMPLEXES OF TITANIUM(IV) [J].
BOYLE, TJ ;
BARNES, DL ;
HEPPERT, JA ;
MORALES, L ;
TAKUSAGAWA, F ;
CONNOLLY, JW .
ORGANOMETALLICS, 1992, 11 (03) :1112-1126
[7]   TITANIUM(IV) AND ZIRCONIUM(IV) TETRAHYDROBORATE MOIETIES SUPPORTED BY A PHENOXO LIGAND [J].
CORAZZA, F ;
FLORIANI, C ;
CHIESIVILLA, A ;
GUASTINI, C .
INORGANIC CHEMISTRY, 1991, 30 (01) :145-148
[8]   CORRELATION OF THE STRUCTURE OF CHIRAL O,O'-BISPHENOL-TI(IV) COMPLEXES WITH LIGAND ELECTRONIC EFFECTS - A RELATIONSHIP BETWEEN LEWIS ACIDITY AND ANGLE STRAIN [J].
COREY, EJ ;
LETAVIC, MA ;
NOE, MC ;
SARSHAR, S .
TETRAHEDRON LETTERS, 1994, 35 (41) :7553-7556
[9]   CYCLIC SILANES - SULFUR-INDUCED PENTACOORDINATION IN A DISILOXANE [J].
DAY, RO ;
PRAKASHA, TK ;
HOLMES, RR ;
ECKERT, H .
ORGANOMETALLICS, 1994, 13 (04) :1285-1293
[10]   A TORSIONALLY CONSTRAINED DIOLATE LIGAND - NOVEL COMPLEXES OF OCTAHYDROBINAPHTHOL WITH TITANIUM(IV) [J].
EILERTS, NW ;
HEPPERT, JA ;
KENNEDY, ML ;
TAKUSAGAWA, F .
INORGANIC CHEMISTRY, 1994, 33 (22) :4813-4814