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Rhodium‐103 NMR of Carboxylate and Thiolate Complexes by Indirect Detection using Phosphorus
Author(s) -
Carlton Laurence
Publication year - 1997
Publication title -
magnetic resonance in chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.483
H-Index - 72
eISSN - 1097-458X
pISSN - 0749-1581
DOI - 10.1002/(sici)1097-458x(199703)35:3<153::aid-omr41>3.0.co;2-w
Subject(s) - chemistry , rhodium , carboxylate , phosphorus , phosphorus 31 nmr spectroscopy , proton nmr , nuclear magnetic resonance spectroscopy , stereochemistry , organic chemistry , catalysis
Fifty four carboxylate and thiolate complexes of rhodium including [Rh(O 2 CR)(PPh 3 ) 3 ] (R=CH 3 , CF 3 ), [Rh 2 (SC 6 F 5 ) 2 (PPh 3 ) 4 ] and derivatives obtained by reaction with hydrogen, pyridine and methyldiphenylphosphine, [Rh(O 2 CArN)(H) 2 (PPh 3 ) 2 ] (O 2 CArN=pyridine‐2‐carboxylate and related chelating ligands) and complexes prepared in situ (many as mixtures) by the reaction of [Rh(H)(PPh 3 ) 4 ] with various thiols were studied by two‐dimensional inverse 103 Rh– 31 P correlated NMR (HMQC). Rhodium chemical shifts were found to fall within the range 840 to ‐422 ppm. Trends in δ 103 Rh for thiolate and carboxylate complexes are similar but not identical, with somewhat lower δ for most of the thiolates, increasing in the approximate order [Rh(SR)(H) 2 (PPh 3 ) 3 ]<[Rh(SR)(PPh 3 ) 3 ], cis ‐[Rh(SR)(PPh 3 ) 2 (py)]<[Rh 2 (SR) 2 (PPh 3 ) 4 ]<[Rh(SR)(H) 2 (PPh 3 ) 2 (py)]<[Rh(SR) 2 (H)(PPh 3 ) 2 (py)]. © 1997 by John Wiley & Sons, Ltd.