TY - JOUR
T1 - Selective dynamics of [Rh(1,5-COD)(bidentate)]BF4 complexes via NMR exchange spectroscopy
AU - Valentini, Massimiliano
AU - Selvakumar, Kumaravel
AU - Wörle, Michael
AU - Pregosin, Paul S.
N1 - Funding Information:
P.S.P. thanks the Swiss National Science Foundation and the ETH Zurich for financial support. We also thank F. Hoffmann–La Roche AG, Basel, for the MeOBiphep ligand, Professor A. Togni for ferrocene ligand 7 as well as Johnson Matthey for the loan of RhCl 3 . Special thanks are due Dr Heinz Rüegger for the loan of complex 14 and for helpful discussions.
PY - 1999/9/25
Y1 - 1999/9/25
N2 - NMR exchange measurements on [Rh(1,5-COD)(bidentate)]BF4 complexes (bidentate = chiral bis-phosphine, a P,N-phosphino-oxazoline, a P,S-phosphito-thioether and a bis-pyrazolylborate) show selective 1,5-COD dynamics which can be superficially attributed to olefin rotation. It is suggested that the mechanism actually involves: (i) M-L1 bond breaking (L1 = N or S-donor); (ii) isomerization of the T-shaped species; (iii) rotation around the remaining M-L2 bond and (iv) recomplexation. The solid state structures of the two compounds [M(1,5-COD)(10)]BF4, M = Rh, Ir and 10=(S,R)-2-[4-(isopropyl)oxazol-2-yl]-2′-diphenylphosphino-1,1′- binaphthyl, were determined by X-ray diffraction methods.
AB - NMR exchange measurements on [Rh(1,5-COD)(bidentate)]BF4 complexes (bidentate = chiral bis-phosphine, a P,N-phosphino-oxazoline, a P,S-phosphito-thioether and a bis-pyrazolylborate) show selective 1,5-COD dynamics which can be superficially attributed to olefin rotation. It is suggested that the mechanism actually involves: (i) M-L1 bond breaking (L1 = N or S-donor); (ii) isomerization of the T-shaped species; (iii) rotation around the remaining M-L2 bond and (iv) recomplexation. The solid state structures of the two compounds [M(1,5-COD)(10)]BF4, M = Rh, Ir and 10=(S,R)-2-[4-(isopropyl)oxazol-2-yl]-2′-diphenylphosphino-1,1′- binaphthyl, were determined by X-ray diffraction methods.
KW - 2 D-exchange NMR
KW - X-ray diffraction
KW - [Rh(1,5-COD)(bidentate)]
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U2 - 10.1016/S0022-328X(99)00329-0
DO - 10.1016/S0022-328X(99)00329-0
M3 - Article
AN - SCOPUS:0000848602
SN - 0022-328X
VL - 587
SP - 244
EP - 251
JO - Journal of Organometallic Chemistry
JF - Journal of Organometallic Chemistry
IS - 2
ER -