DYNAMIC STEREOCHEMISTRY IN THE TITANOCENE SERIES WITH CENTRAL AND PLANAR CHIRALITY - X-RAY STRUCTURE AND RELATIVE CONFIGURATION OF THE RACEMIC FORM (MP 186-DEGREES-C) OF [(ETA(5)-1-ME-2-(PRC5H3)-PR-I)(ETA(5)-C5H5)TI(2,6-ME(2)C(6)H(3)O)CL]

被引：2

作者：

BESANCON, J

SZYMONIAK, J

MOISE, C

TOUPET, L

TRIMAILLE, B

机构：

[1] GRP MAT CONDENSEE & MAT,CNRS,URA 804,F-35042 RENNES,FRANCE

[2] UFR SCI & TECH,DEPT CHIM,F-25030 BESANCON,FRANCE

来源：

JOURNAL OF ORGANOMETALLIC CHEMISTRY | 1995年 / 491卷 / 1-2期

关键词：

TITANIUM; TITANOCENE; CHIRALITY; X-RAY DIFFRACTION;

D O I：

10.1016/0022-328X(94)05242-4

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

The dynamic stereochemistry of two substitution reactions [(i) and (ii)] for the thiocyanate and isocyanate complexes of titanocene has been reinvestigated. [GRAPHICS] The metathesis reaction (ii) has been shown to be chemoselective and stereospecific with inversion of the configuration at the titanium for X = NCO and retention for X = NCS. This stereochemical behaviour contrasts with that proposed previously, i.e. inversion of configurations for both X = NCO and X = NCS. The present result is unambiguously supported by the crystallographic structure of the racemic compound 1c' (X = Cl, m.p. 186 degrees C), which was chosen as the starting stereochemical reference. The complex 1c' crystallizes in the monoclinic system, space group C-c. Two well-characterized quasi-eclipsed and staggered conformational forms of the complex 1c' are presented. According to Seebach's nomenclature, this structure corresponds to the u(Ti, p) configuration.

引用

页码：31 / 39

页数：9

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