The photoisomerisation (lambda=400nm) of [Tp(Me2)Rh (eta(4)-1,5-COD)] (1), (Tp(Me2)=hydrotris(3,5-dimethyl)pyrazolyl borate, 1,5-COD=1,5-cyclooctadiene) to [Tp(Me2)Rh (eta(4)-1,3-COD)] (2) is reported. The photoreaction is an intramolecular (3,4) hydrogen shift of the coordinated 1,5-COD possibly involving an allylrhodium(III) intermediate. The selective photolysis of complex 2 with 336 nm light causes the dissociation of 1,3-COD forming the organometallic fragment {Tp(Me2)Rh} (A) as its primary photoproduct. Fragment A is a versatile entry point in the photochemical preparation of new hydride Rh(III) complexes.
Photochemistry of rhodium(I) olefin complexes containing the (hydro)tris(pyrazolyl)borate ligand
BOARETTO, Rita;FERRARI, Arlen;SOSTERO, Silvana;TRAVERSO, Orazio
2000
Abstract
The photoisomerisation (lambda=400nm) of [Tp(Me2)Rh (eta(4)-1,5-COD)] (1), (Tp(Me2)=hydrotris(3,5-dimethyl)pyrazolyl borate, 1,5-COD=1,5-cyclooctadiene) to [Tp(Me2)Rh (eta(4)-1,3-COD)] (2) is reported. The photoreaction is an intramolecular (3,4) hydrogen shift of the coordinated 1,5-COD possibly involving an allylrhodium(III) intermediate. The selective photolysis of complex 2 with 336 nm light causes the dissociation of 1,3-COD forming the organometallic fragment {Tp(Me2)Rh} (A) as its primary photoproduct. Fragment A is a versatile entry point in the photochemical preparation of new hydride Rh(III) complexes.File in questo prodotto:
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