Document Detail


Thorium-mediated ring-opening of tetrahydrofuran and the development of a new thorium starting material: preparation and chemistry of ThI(4)(DME)(2).
MedLine Citation:
PMID:  23027565     Owner:  NLM     Status:  Publisher    
Abstract/OtherAbstract:
The thorium(iv) tetraiodide complex ThI(4)(DME)(2) () (DME = 1,2-dimethoxyethane) has been prepared in high yield by reacting the corresponding chloride complex ThCl(4)(DME)(2) with an excess of trimethylsilyl iodide (Me(3)SiI) in toluene. This new route avoids the use of thorium metal as a reagent. ThI(4)(DME)(2) () exhibits excellent thermal stability compared to ThI(4)(THF)(4) (), which undergoes rapid ring-opening of THF at ambient temperature to yield the iodobutoxide complex ThI(3)[O(CH(2))(4)I](THF)(3) (). Subsequent ligand-exchange between and DME affords ThI(3)[O(CH(2))(4)I](DME)(2) (), which can be converted to with Me(3)SiI. Salt metathesis between and K(L(Me)) (L(Me) = (2,6-(i)Pr(2)C(6)H(3))NC(Me)CHC(Me)N(2,6-(i)Pr(2)C(6)H(3))) cleanly gives (L(Me))ThI(2)[O(CH(2))(4)I](THF) (), which is a rare example of a thorium β-diketiminate complex. Complexes , , and represent the first reported examples of THF ring-opening mediated by thorium. The synthetic utility of ThI(4)(DME)(2) () is demonstrated by preparation of thorium(iv) alkoxide, amide, and organometallic compounds.
Authors:
Nicholas E Travia; Marisa J Monreal; Brian L Scott; Jaqueline L Kiplinger
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Publication Detail:
Type:  JOURNAL ARTICLE     Date:  2012-10-2
Journal Detail:
Title:  Dalton transactions (Cambridge, England : 2003)     Volume:  -     ISSN:  1477-9234     ISO Abbreviation:  Dalton Trans     Publication Date:  2012 Oct 
Date Detail:
Created Date:  2012-10-2     Completed Date:  -     Revised Date:  -    
Medline Journal Info:
Nlm Unique ID:  101176026     Medline TA:  Dalton Trans     Country:  -    
Other Details:
Languages:  ENG     Pagination:  -     Citation Subset:  -    
Affiliation:
Los Alamos National Laboratory, Mail Stop J-514, Los Alamos, NM 87545, USA. kiplinger@lanl.gov.
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