The photochem. behavior of a no. of flyover-bridge iron complexes I (R = R1 = R2 = R3 = Me, Et, Ph; R = R3 = Me, R1 = R2 = Ph; R = R3 = Ph, R1 = R2 = Me; R = R2 = Ph, R1 = R3 = Me) is discussed with regard to their electronic structure. In the case of I (R-R1 = Ph) the overall photochem. event is the formation of an unsatd. species upon CO loss, which evolves, in the absence of any Lewis bases, the fragments of [Fe(CO)3{(PhC2Ph)2CO}], C4Ph4CO, and [Fe(CO)5]. Photosubstitution of CO by phosphine occurs very rapidly and proceeds stereospecifically in a pseudo-axial position as assessed by 13C NMR studies. I exhibit photocatalytic activity toward olefin isomerization and, interestingly, this reaction can be activated simply by sunlight exposure. The dienone chain clasps the metal-metal bond, preventing complex decompn. and acts as a good sensitizer for the sunlight.

Photochemical and photocatalytic behavior of 'flyover-bridge' complexes

BOTTA, Mauro;GOBETTO, Roberto;
1988-01-01

Abstract

The photochem. behavior of a no. of flyover-bridge iron complexes I (R = R1 = R2 = R3 = Me, Et, Ph; R = R3 = Me, R1 = R2 = Ph; R = R3 = Ph, R1 = R2 = Me; R = R2 = Ph, R1 = R3 = Me) is discussed with regard to their electronic structure. In the case of I (R-R1 = Ph) the overall photochem. event is the formation of an unsatd. species upon CO loss, which evolves, in the absence of any Lewis bases, the fragments of [Fe(CO)3{(PhC2Ph)2CO}], C4Ph4CO, and [Fe(CO)5]. Photosubstitution of CO by phosphine occurs very rapidly and proceeds stereospecifically in a pseudo-axial position as assessed by 13C NMR studies. I exhibit photocatalytic activity toward olefin isomerization and, interestingly, this reaction can be activated simply by sunlight exposure. The dienone chain clasps the metal-metal bond, preventing complex decompn. and acts as a good sensitizer for the sunlight.
1988
-
2519
2524
photochemistry; flyover bridge iron complex; photocatalysis; isomerization
Osella, Domenico; Botta, Mauro; Gobetto, Roberto; Amadelli, Rossano; Carassiti, Vittorio
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Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/2318/48154
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