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Some catalytic and stoichiometric re...

Xin, Shixuan.

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Some catalytic and stoichiometric reactions of titanocene and chiral ansa-titanocene derivatives with silanes and siloxanes.

Record Type:	Language materials, printed : Monograph/item
Title/Author:	Some catalytic and stoichiometric reactions of titanocene and chiral ansa-titanocene derivatives with silanes and siloxanes./
Author:	Xin, Shixuan.
Description:	236 p.
Notes:	Adviser: John F. Harrod.
Contained By:	Dissertation Abstracts International57-04B.
Subject:	Chemistry, Inorganic. -
Online resource:	http://pqdd.sinica.edu.tw/twdaoapp/servlet/advanced?query=NN08169
ISBN:	9780612081697

Some catalytic and stoichiometric reactions of titanocene and chiral ansa-titanocene derivatives with silanes and siloxanes.
Xin, Shixuan.

Some catalytic and stoichiometric reactions of titanocene and chiral ansa-titanocene derivatives with silanes and siloxanes. - 236 p.

Adviser: John F. Harrod.

Thesis (Ph.D.)--McGill University (Canada), 1995.

Several types of catalytic and stoichiometric reactions of titanocenes and chiral ansa-titanocenes were studied.

ISBN: 9780612081697Subjects--Topical Terms:

517253
Chemistry, Inorganic.

Some catalytic and stoichiometric reactions of titanocene and chiral ansa-titanocene derivatives with silanes and siloxanes.
LDR:02880nam 2200289 a 45 001 948346
005 20110524
008 110524s1995 eng d
020 $a 9780612081697
035 $a (UMI)AAINN08169
035 $a AAINN08169
040 $a UMI $c UMI
100 1 $a Xin, Shixuan. $3 1271806
245 1 0 $a Some catalytic and stoichiometric reactions of titanocene and chiral ansa-titanocene derivatives with silanes and siloxanes.
300 $a 236 p.
500 $a Adviser: John F. Harrod.
500 $a Source: Dissertation Abstracts International, Volume: 57-04, Section: B, page: 2561.
502 $a Thesis (Ph.D.)--McGill University (Canada), 1995.
520 $a Several types of catalytic and stoichiometric reactions of titanocenes and chiral ansa-titanocenes were studied.
520 $a Dimethyltitanocene (DMT) and rac- (EBTHI) TiMe$\sb2$ (EBTHI = ethylene-1,2-bis (4,5,6,7-tetrahydro-1-indenyl)) are effective catalyst precursors for hydrosilation of a variety of ketones when using in conjunction with secondary silanes. A catalyst generated by in situ reaction of enantiomerically pure S- (EBTHI) TiX$\sb2$ (X = Cl, 1/2(S-1,1$\sp\prime$-binaphthyl-2,2$\sp\prime$-diolate)) with MeLi catalyzes hydrosilation of dialkyl ketones to give, after hydrolysis, the enantioenriched secondary alcohols in up to 70% ee. This result compares favorably with the best chiral-phosphine/Rh catalysts for asymmetric hydrosilation of dialkyl ketones. DMT and rac-(EBTHI) TiMe$\sb2$ are also very active catalyst precursors for cross dehydrocoupling/co-intramolecular hydrosilation of allylic and homoallylic alcohols with secondary silanes. This is the first time such reactions catalyzed by group 4 metallocenes have been reported.
520 $a Photochemical stoichiometric reactions of DMT and rac-(EBTHI) TiMe$\sb2$ with hydrosiloxanes in the presence of pyridine produce two novel Ti(III)-pyridine complexes Cp$\sb2 $t i(Me)(Py) and rac-(EBTHI) Ti(Me)(Py). Their structures were characterized by X-ray crystallography and EPR spectroscopy. Stoichiometric reaction of rac-(EBTHI) TiMe$\sb2$ with phenylmethylsilane gives a Ti(III) hydride dimer, rac-((EBTHI)Ti($\mu$-H)) $\sb2$, which is the first structurally characterized Ti(III) hydride dimer without a bridging organic ligand. EPR spectroscopic study revealed that the dimer exists in equilibrium with its monomer in solution. Reaction of this hydride dimer in the presence of excess phenylphosphine produces a Ti(IV) diphosphanediyl complex, rac-(EBTHI) Ti(PPh)$\sb2$, in quantitative yield. The structure of rac-(EBTHI) Ti(PPh)$\sb2$ was also characterized by X-ray crystallography.
590 $a School code: 0781.
650 4 $a Chemistry, Inorganic. $3 517253
690 $a 0488
710 2 0 $a McGill University (Canada). $3 1018122
773 0 $t Dissertation Abstracts International $g 57-04B.
790 $a 0781
790 1 0 $a Harrod, John F., $e advisor
791 $a Ph.D.
792 $a 1995
856 4 0 $u http://pqdd.sinica.edu.tw/twdaoapp/servlet/advanced?query=NN08169