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

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

doi:10.1016/S0022-328X(99)00329-0

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

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

^*Corresponding author for this work

Research output: Contribution to journal › Article › peer-review

40 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 language	English
Pages (from-to)	244-251
Number of pages	8
Journal	Journal of Organometallic Chemistry
Volume	587
Issue number	2
DOIs	https://doi.org/10.1016/S0022-328X(99)00329-0
Publication status	Published - Sep 25 1999
Externally published	Yes

Keywords

2 D-exchange NMR
X-ray diffraction
[Rh(1,5-COD)(bidentate)]

ASJC Scopus subject areas

Biochemistry
Physical and Theoretical Chemistry
Organic Chemistry
Inorganic Chemistry
Materials Chemistry

Access to Document

10.1016/S0022-328X(99)00329-0

Cite this

@article{3c75ac33c3284677ae72289af384d73b,

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

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.",

keywords = "2 D-exchange NMR, X-ray diffraction, [Rh(1,5-COD)(bidentate)]",

author = "Massimiliano Valentini and Kumaravel Selvakumar and Michael W{\"o}rle and Pregosin, {Paul S.}",

note = "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 MeOBiphep 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 R{\"u}egger for the loan of complex 14 and for helpful discussions.",

year = "1999",

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doi = "10.1016/S0022-328X(99)00329-0",

language = "English",

volume = "587",

pages = "244--251",

journal = "Journal of Organometallic Chemistry",

issn = "0022-328X",

publisher = "Elsevier",

number = "2",

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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 MeOBiphep 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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