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Synthesis and molecular structures of 1‐chloro‐1‐silacyclopent‐2‐enes. Combination of 1,2‐hydroboration, 1,1‐organoboration and protodeborylation
Author(s) -
Khan Ezzat,
Kempe Rhett,
Wrackmeyer Bernd
Publication year - 2009
Publication title -
applied organometallic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.53
H-Index - 71
eISSN - 1099-0739
pISSN - 0268-2605
DOI - 10.1002/aoc.1482
Subject(s) - chemistry , hydroboration , acetic acid , nonane , nuclear magnetic resonance spectroscopy , crystal structure , density functional theory , stereochemistry , computational chemistry , medicinal chemistry , crystallography , organic chemistry , catalysis
The reaction of alkyn‐1‐yl(chloro)(methyl)vinyl‐ and alkyn‐1‐yl(chloro)(phenyl)‐vinylsilane with 9‐borabicyclo[3.3.1]nonane (9‐BBN) afforded selectively 1‐silacyclopent‐2‐ene derivatives containing a SiCl function, as a result of consecutive 1,2‐hydroboration and 1,1‐organoboration. Protodeborylation with acetic acid left the SiCl functions in various 1‐silacyclopent‐2‐enes untouched, whereas acetic acid in the presence of dipropylamine led to conversion of the SiCl into the SiOAc function. New starting materials and all products were characterized in solution by multinuclear NMR spectroscopy ( 1 H, 11 B, 13 C and 29 Si NMR), and the molecular structures of two 1‐silacyclopent‐2‐ene derivatives were determined by X‐ray analysis. The gas phase geometries of 1‐silacyclopent‐2‐enes were optimized by DFT calculations [B3LYP/6‐311 + G(d,p) level of theory], found to be in reasonable agreement with the results of the crystal structure determination, and NMR parameters were calculated at the same level of theory. Copyright © 2009 John Wiley & Sons, Ltd.