Document Detail

Internally versus externally solvated derivatives of doubly bridged 1,4-dilithio-2-butene: structures and dynamic behavior. A "T" shaped dimeric cluster in the solid state.
MedLine Citation:
PMID:  23289873     Owner:  NLM     Status:  PubMed-not-MEDLINE    
X-ray crystallographic NMR and calculational modeling studies using B3LYP/6-311G* of selected dilithium derivatives of the 1,3-butadiene dianion including cis-dilithio-1,4-bis(TMS)-2-butene·(TMEDA)(2)2, internally solvated cis-dilithio-1,4-bis[bis(2-methoxyethyl)aminomethyldimethylsilyl]-2-butene 5, and using only modeling, 1,4-dilithio-2-butene·(TMEDA)(2)9 reveal remarkably similar structural and NMR parameters. In the solid, 5 consists of unusual "T" shaped dynamic clusters. In all three bridging lithiums are sited between 1.8 and 1.9 Å normal to the centroids of opposite faces of the near coplanar of the 2-butene component. Typical bond lengths of the latter are 1.458 ± 0.004, 1.385 ± 0.006, and 1.459 ± 0.003 Å, for C1-C2, C2-C3, and C3-C4, respectively. The (13)C chemical shifts lie within the ranges δ 21 ± 0.5, 99 ± 0.7, 99 ± 0.7 and 21 ± 0.5 for C1, C2 and C3 together, and C4, respectively. Dynamic (13)C NMR provides activation parameters for nitrogen inversion in 2 and 5, overall molecular inversion of 5, and conformational interconversion of 2.
Gideon Fraenkel; Xiao Chen; Albert Chow; Judith Gallucci
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Publication Detail:
Type:  Journal Article; Research Support, Non-U.S. Gov't     Date:  2013-01-14
Journal Detail:
Title:  The Journal of organic chemistry     Volume:  78     ISSN:  1520-6904     ISO Abbreviation:  J. Org. Chem.     Publication Date:  2013 Feb 
Date Detail:
Created Date:  2013-02-01     Completed Date:  2013-08-09     Revised Date:  2014-01-02    
Medline Journal Info:
Nlm Unique ID:  2985193R     Medline TA:  J Org Chem     Country:  United States    
Other Details:
Languages:  eng     Pagination:  1149-56     Citation Subset:  -    
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Erratum In:
J Org Chem. 2013 Nov 15;78(22):11627

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