TY - JOUR
T1 - Photochemical and photocatalytic behaviour of 'flyover-bridge' complexes
AU - Osella, Domenico
AU - Botta, Mauro
AU - Gobetto, Roberto
AU - Amadelli, Rossano
AU - Carassiti, Vittorio
PY - 1988
Y1 - 1988
N2 - The photochemical behaviour of a number of flyover-bridge complexes [Fe2(CO)6{(RC2R)2CO}] is discussed with regard to their electronic structure. In the case of [Fe 2(CO)6{(PhC2Ph)2CO}] the overall photochemical event is the formation of an unsaturated species upon CO loss, which evolves, in the absence of any Lewis bases, to the fragments [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 n.m.r. studies. The title complexes 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 decomposition and acts as a good sensitizer for the sunlight.
AB - The photochemical behaviour of a number of flyover-bridge complexes [Fe2(CO)6{(RC2R)2CO}] is discussed with regard to their electronic structure. In the case of [Fe 2(CO)6{(PhC2Ph)2CO}] the overall photochemical event is the formation of an unsaturated species upon CO loss, which evolves, in the absence of any Lewis bases, to the fragments [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 n.m.r. studies. The title complexes 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 decomposition and acts as a good sensitizer for the sunlight.
UR - http://www.scopus.com/inward/record.url?scp=37049086568&partnerID=8YFLogxK
U2 - 10.1039/DT9880002519
DO - 10.1039/DT9880002519
M3 - Article
SN - 1472-7773
SP - 2519
EP - 2524
JO - Journal of the Chemical Society. Dalton Transactions
JF - Journal of the Chemical Society. Dalton Transactions
IS - 10
ER -