Document Detail

Synthesis and Reactivity of Boron-, Silicon-, and Tin-Bridged ansa-Cyclopentadienyl-Cycloheptatrienyl Titanium Complexes (Troticenophanes).
MedLine Citation:
PMID:  20803585     Owner:  NLM     Status:  In-Data-Review    
A novel one-pot method was developed for the preparation of [Ti(η(5) -C(5) H(5) )(η(7) -C(7) H(7) )] (troticene, 1) by reaction of sodium cyclopentadienide (NaCp) with [TiCl(4) (thf)(2) ], followed by reduction of the intermediate [(η(5) -C(5) H(5) )(2) TiCl(2) ] with magnesium in the presence of cycloheptatriene (C(7) H(8) ). The [n]troticenophanes 3 (n=1), 4, 8, 10 (n=2), and 11 (n=3) were synthesized by salt elimination reactions between dilithiated troticene, [Ti(η(5) -C(5) H(4) Li)(η(7) -C(7) H(6) Li)]⋅pmdta (2) (pmdta=N,N',N',N'',N''-pentamethyldiethylenetriamine), and the appropriate organoelement dichlorides Cl(2) Sn(Mes)(2) (Mes=2,4,6-trimethylphenyl), Cl(2) Sn(2) (tBu)(4) , Cl(2) B(2) (NMe(2) )(2) , Cl(2) Si(2) Me(4) , and (ClSiMe(2) )(2) CH(2) , respectively. Their structural characterization was carried out by single-crystal X-ray diffraction and multinuclear NMR spectroscopy. The stanna[1]- and stanna[2]troticenophanes 3 and 4 represent the first heteroleptic sandwich complexes bearing Sn atoms in the ansa bridge. The reaction of 3 with [Pt(PEt(3) )(3) ] resulted in regioselective insertion of the [Pt(PEt(3) )(2) ] fragment into the SnC(ipso) bond between the tin atom and the seven-membered ring, which afforded the platinastanna[2]troticenophane 5. Oxidative addition was also observed upon treatment of 4 with elemental sulfur or selenium, to produce the [3]troticenophanes [Ti(η(5) -C(5) H(4) SntBu(2) )(η(7) -C(7) H(6) SntBu(2) )E] (6: E=S; 7: E=Se). The BB bond of the bora[2]troticenophane 8 was readily cleaved by reaction with [Pt(PEt(3) )(3) ] to form the corresponding oxidative addition product [Ti(η(5) -C(5) H(4) BNMe(2) )(η(7) -C(7) H(6) BNMe(2) )Pt(PEt(3) )(2) ] (9). The solid-state structures of compounds 5, 6, and 9 were also determined by single-crystal X-ray diffraction.
Holger Braunschweig; Marco Fuß; Swagat K Mohapatra; Katharina Kraft; Thomas Kupfer; Melanie Lang; Krzysztof Radacki; Constantin G Daniliuc; Peter G Jones; Matthias Tamm
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Publication Detail:
Type:  Journal Article     Date:  2010-08-27
Journal Detail:
Title:  Chemistry (Weinheim an der Bergstrasse, Germany)     Volume:  16     ISSN:  1521-3765     ISO Abbreviation:  Chemistry     Publication Date:  2010 Oct 
Date Detail:
Created Date:  2012-10-05     Completed Date:  -     Revised Date:  -    
Medline Journal Info:
Nlm Unique ID:  9513783     Medline TA:  Chemistry     Country:  Germany    
Other Details:
Languages:  eng     Pagination:  11732-43     Citation Subset:  IM    
Copyright Information:
Copyright © 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
Institut für Anorganische Chemie, Julius Maximilians-Universität Würzburg, Am Hubland, 97074 Würzburg (Germany), Fax: (+49) 931-31-84623.
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