Photoexcitation of iron-allyl complexes (η5: η1-C5H4CH2CH2PPh2Fe(CO)(η1-CH2CR=CH2) (R = H, CH3) which contains a tethered phosphine ligand

Organometallic photochemistry at the end of its first century

“…The mechanism of this reaction for CpW(CO) 3 (g 1 -C 3 H 5 ) was confirmed using Ar matrix photochemistry [13]. Wang and Lai have demonstrated that photolysis of the chelated species, (g 5 ,j 1 -C 5 H 4 C 2 H 4 PPh 2 )Fe(CO)(g 1 -C 3 H 4 R), where R ‚ H, Me, yields the corresponding g 3 -allyl derivatives upon photochemical CO-loss [14]. Similarly, g 1 -benzyl ligands have been observed to form g 3 -benzyl species upon CO loss [15].…”

Intramolecular Dehydrofluorinative Coupling of η5-Pentamethylcyclopentadienyl and Pentafluorophenylphosphine Ligands in Rhodium Complexes

“…For a number of cases these expectations have been realized. For example, zirconium complexes of trifunctional cyclopentadienyl-diphosphines have been isolated, the unlinked cyclopentadienide phosphine analogues of which are either unknown or unstable; [{η 5 ,κ P -indenyl-CH 2 CH 2 PPh 2 }RhMe(CO)]BF 4 reacts with 1-phenylpropyne at room temperature, affording [{η 5 ,κ P -indenyl-CH 2 CH 2 PPh 2 }RhMe{C(Ph)C(Me)C(Me)O}]BF 4 , whereas under the same conditions [(η 5 -indenyl)RhMe(CO)(PPh 3 )]BF 4 does not react; and the high diastereoselectivity shown by [{η 5 ,κ P -C 5 H 2 (CO 2 CH 2 CH 2 PPh 2 )MeR-2,4}Ru(NCMe) 2 ]PF 6 in its ligand substitution reactions with phosphines and phosphites is in contrast to the low diastereoselectivity shown by [{η 5 -C 5 H 2 (CO 2 Et)MeR-2,4}Ru(NCMe) 2 {P(OMe) 3 }]PF 6 . Despite the advantages offered by these ligands, the number of reports of complexes of chelating hybrid cyclopentadienyl-phosphine ligands is somewhat limited .…”