Selective dynamics of [Rh(1,5-COD)(bidentate)]BF4 complexes via NMR exchange spectroscopy

Massimiliano Valentini, Kumaravel Selvakumar, Michael Wörle, Paul S. Pregosin

Research output: Contribution to journal › Article

38 Citations (Scopus)

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 languageEnglish
Pages (from-to)244-251
Number of pages8
JournalJournal of Organometallic Chemistry
Volume587
Issue number2
Publication statusPublished - Sep 25 1999

Fingerprint

crack opening displacement
phosphine
Magnetic Resonance Spectroscopy
Nuclear magnetic resonance
Spectroscopy
nuclear magnetic resonance
Isomerization
spectroscopy
Olefins
Alkenes
Sulfides
phosphines
X-Ray Diffraction
X ray diffraction
isomerization
alkenes
solid state
diffraction
1,3-cyclooctadiene
x rays

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

Valentini, M, Selvakumar, K, Wörle, M & Pregosin, PS 1999, 'Selective dynamics of [Rh(1,5-COD)(bidentate)]BF4 complexes via NMR exchange spectroscopy', Journal of Organometallic Chemistry, vol. 587, no. 2, pp. 244-251.
Valentini M, Selvakumar K, Wörle M, Pregosin PS. Selective dynamics of [Rh(1,5-COD)(bidentate)]BF4 complexes via NMR exchange spectroscopy. Journal of Organometallic Chemistry. 1999 Sep 25;587(2):244-251.
Valentini, Massimiliano ; Selvakumar, Kumaravel ; Wörle, Michael ; Pregosin, Paul S. / Selective dynamics of [Rh(1,5-COD)(bidentate)]BF4 complexes via NMR exchange spectroscopy. In: Journal of Organometallic Chemistry. 1999 ; Vol. 587, No. 2. pp. 244-251.
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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.

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