Rotameric transformations in the photochemistry of TpM(CO)2(η(3)-C3H4R), where Tp = tris(pyrazolyl)borate, M = Mo or W, and R = H or Me.
DALTON TRANSACTIONS(2015)
Abstract
Low energy photolysis of TpM(CO)(2)(eta(3)-C3H4R), where Tp = tris(pyrazolyl)borate, M = Mo or W, and R = 2-H or 2-Me in PVC matrices at 85 K results in exo/gauche isomerism of the allyl ligand. This transformation comes in contrast to the behaviour observed in cyclopentadienyl analogues which undergo exo/endo isomerism. DFT computations reveal an eta(3) -->eta(1)* -->eta(3) mechanism for the allyl rotameric interconversion where the eta(1)*-allyl intermediate is generated upon MLCT excitation.
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Key words
Electrochemical Conversion
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