Abstract
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.
| Original language | English |
|---|---|
| Pages (from-to) | 244-251 |
| Number of pages | 8 |
| Journal | Journal of Organometallic Chemistry |
| Volume | 587 |
| Issue number | 2 |
| Publication status | Published - Sep 25 1999 |
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Keywords
- 2 D-exchange NMR
- [Rh(1,5-COD)(bidentate)]
- X-ray diffraction
ASJC Scopus subject areas
- Biochemistry
- Physical and Theoretical Chemistry
- Organic Chemistry
- Inorganic Chemistry
- Materials Chemistry
Cite this
Selective dynamics of [Rh(1,5-COD)(bidentate)]BF4 complexes via NMR exchange spectroscopy. / Valentini, Massimiliano; Selvakumar, Kumaravel; Wörle, Michael; Pregosin, Paul S.
In: Journal of Organometallic Chemistry, Vol. 587, No. 2, 25.09.1999, p. 244-251.Research output: Contribution to journal › Article
}
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.
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 - [Rh(1,5-COD)(bidentate)]
KW - X-ray diffraction
UR - http://www.scopus.com/inward/record.url?scp=0000848602&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=0000848602&partnerID=8YFLogxK
M3 - Article
AN - SCOPUS:0000848602
VL - 587
SP - 244
EP - 251
JO - Journal of Organometallic Chemistry
JF - Journal of Organometallic Chemistry
SN - 0022-328X
IS - 2
ER -