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Geminal 2J(29Si-O-29Si) couplings in oligosiloxanes and their relation to direct 1J(29Si-13C) couplings

✍ Scribed by Milan Kurfürst; Vratislav Blechta; Jan Schraml

Publisher
John Wiley and Sons
Year
2011
Tongue
English
Weight
308 KB
Volume
49
Category
Article
ISSN
0749-1581

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✦ Synopsis

Abstract

Absolute values of (79) geminal ^2^J(^29^Si‐O‐^29^Si) couplings were measured in an extensive series of (55) unstrained siloxanes dissolved in chloroform‐d. Signs of ^2^J(^29^Si‐O‐^29^Si) in some (9) silicon hydrides were determined relative to ^1^J(^29^Si‐^1^H) which are known to be negative. It is supposed that positive sign of the ^2^J(^29^Si‐O‐^29^Si) coupling found in all studied hydrides is common to all siloxanes. Theoretical calculations for simple model compounds failed to reproduce this sign and so their predictions of bond length and angle dependences cannot be taken as reliable. Useful empirical correlations were found between the ^2^J(^29^Si‐O‐^29^Si) couplings on one side and the total number m of oxygen atoms bonded to the silicon atoms, sum of ^29^Si chemical shifts or product of ^1^J(^29^Si‐^13^C) couplings on the other side. The significance of these correlations is briefly discussed. Copyright © 2011 John Wiley & Sons, Ltd.

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