Metal atom synthesis of iron diene phosphite complexes

Chemistry derived from ruthenium atoms. 1. Dimerization of coordinated 2,3-dimethylbutadiene ligands in M(CO)(diene)2 complexes (M = Ru, Fe). Crystal structure of dicarbonyl[(1,2,3-.eta.:6,7,8-.eta.)-2,3,6,7-tetramethyloctadienediyl]ruthenium

“…Hence, Ru(PPh3) (^-butadiene) 2 and Fe(CO)(?74-butadiene)2 have been reported to react with a variety of phosphines to produce ML^-C^He) type complexes in high yield. 30 Alternatively, Ittel et al 28 have noted that Fe(P(OMe)3)(?/4-isoprene)2 is not susceptible to further phosphite addition. Furthermore, the spectroscopic identification of several ML2(?/4-diene)(?…”

Structural consequences of electron-transfer reactions. 5. Electrochemically induced isomerizations of (cyclooctadiene)- and (cyclooctatetraene)cobalt compounds

“…(COD)Fe(PR3)3 complexes synthesized in metal atom reactors have been reported by groups at Bristol36 and at Du Pont. 37,38 In the cocondensation reaction of either 1,5-or 1,3-COD, P(OMe)3, and iron, only (l,3-COD)Fe[P(OMe)3]3 is isolated, but the 1,5-isomer presumably forms initially and then rearranges to the more stable 1,3-isomer.38 Both 1,3-and 1,5isomers of (COD)Fe(PF3)3 can be isolated, depending on which isomer of the hydrocarbon is used in the cocondensation reaction.…”

Hydrogen-transfer reactions catalyzed by low-valent, tertiary phosphine complexes of zirconium. Molecular structure of hydrido(.eta.5-cyclooctadienyl)bis[1,2-bis(dimethylphosphino)ethane]zirconium

“…For example, cocondensation of 1,3-cyclohexadiene, P(OMe)3, and iron atoms affords Fe(rr4-C6H8)[P(OMe)3]3 and FeH(r/5-C6H7)[P(OMe)3]2. 35 Further, coordinatively unsaturated group 4 complexes appear to be particularly reactive toward sp3 CH bonds, as suggested by reactions involving insertion into alkyl C-H groups attached to coordinated cyclopentadienyl ligands.36…”

“…;5-cyclohexadienyl hydride. 35,39,42 A plausible mechanism is shown in Scheme I. The first-order dependence on cyclohexadiene concentration suggests a step involving association of substrate is the slowest.…”