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Three‐centre RhHSn bonds: an NMR study of the effects of varying the electron density on rhodium
Author(s) -
Carlton Laurence
Publication year - 2001
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.120
Subject(s) - chemistry , rhodium , pyridine , stereochemistry , crystallography , ligand (biochemistry) , electron density , electron , medicinal chemistry , catalysis , organic chemistry , receptor , biochemistry , physics , quantum mechanics
Abstract The complexes [Rh(X)(H)(SnPh 3 )(PPh 3 )(L)] (X = NCBPh 3 (a), N(CN) 2 (b), NCS (c), NCO (d), N 3 (e); L = 1‐methylimidazole) ( 1 ) show systematic changes in δ ( 119 Sn), δ ( 103 Rh), J ( 119 Sn– 1 H) and J ( 119 Sn– 103 Rh) that are related to the electron‐donating properties of X. As X becomes more electron‐rich, δ ( 103 Rh), J ( 119 Sn– 1 H) and J ( 119 Sn– 103 Rh) increase and δ 119 Sn) decreases. The related complexes trans ‐[Rh(X)(H)(SnPh 3 )(PPh 3 ) 2 (L)] (X = N(CN) 2 , NCO; L = 4‐carboxymethylpyridine (x), pyridine (y) and 4‐dimethylaminopyridine (z)) ( 2 ), show a continuation of the trends in δ ( 119 Sn) and J ( 119 Sn– 1 H), but not δ ( 103 Rh) or J ( 119 Sn– 103 Rh). Data for 1 and 2 show that within certain limits of type of ligand varied (X = N‐donor, L = a pyridine) and coordination geometry, the response of δ ( 119 Sn) and J ( 119 Sn– 1 H) to changes in electron density on rhodium is largely independent of the means by which the change is effected.Copyright © 2001 John Wiley & Sons, Ltd.