π-Perfluoroallyltricarbonylcobalt: Synthesis and Reaction with Triphenylphosphine

Abstract

Perfluoroallyl iodide reacts with Zn[Co(CO)4]2 to give π-C3F5Co(CO)3 and CF3CF=CFCo-(CO)4. The reaction of π -C3F5Co(CO)3 with PPh3 gives two products; trans-CF3CF=CFCo(CO)3PPh3 and a compound tentatively identified as cis-CF2=CFCF2Co(CO)3PPh3; (cis and trans refer to configuration about cobalt). Infrared and n.m.r. data for the compounds are reported.

Photochemistry of (η3-allyl)tricarbonyecobaet in frozen gas matrices at 12 K. Infrared spectroscopic evidence for the formation of (η3-allyl) dicarbonylcobalt, (η3-allyl)dicarbonyl(dinitrogen)cobalt, (σ-allyl)tetracarbonylcobalt, and tetracarbonylcobalt complexes

“…The shift of the bands of [C~(q~-alIyl)(CO)~] (Table 1) to lower wavenumbers than those of [C~($-allyl)(CO)~] rules out this species, i. 4 34 In matrix isolation studies when species are formed which could have sixteen-or twentyelectron configurations and which contain ligands that can rearrange or change their hapticity, then rearrangement in order to achieve an eighteen-electron configuration occurs. For example, photolysis of [Mn(CH3CO)(CO),] even in CO matrices at 12 K leads to the transient formation of [Mn-(CH,CO)(CO),] (sixteen-electron), but this species immediately goes on to [Mn(CH3)(CO)5] (eighteen-electron) by a methyl m i g r a t i ~n .…”