Mechanism of attack by trialkylphosphines on dicarbonyl(dienyl)iodo-iron complexes

Nucleophilic addition to coordinated cyclic .pi.-hydrocarbons: mechanistic and synthetic studies

“…These processes have been shown to occur via two distinct steps (Scheme III). 39 The kinetically favored addition (fex) to the C6H7 ligand has a much lower AHi value (32 kJ mol-1) than the subsequent iodide substitution process (AH2* = 91 kJ mol-1). In certain cases, such as the reactions of trialkylphosphines with cations Mn(CO)3(?j-C6H6)+ and Mo(CO)3(?j-C7H7)+, where only carbonyl or ^-hydrocarbon displaced products were isolated by others,13,40 (2) [Fe(CO)2(N-0)(C4H4)]PF6; (3) [Ru(C6H6)2](PF6)2; (4) [Cr(CO)3(C7H7)]BF4; (5) [Fe(CO)(NO)(PPh3)(C4H4)]PF6; (6) [Mn(CO)3(C6H6)]PF6.…”

Addition of anilines to the [Fe(CO)3(1–5-η-C7H9)]BF4complex, and the ‘Ordered Transition State Mechanism’

“…These results are compared with results reported earlier for amine additions to the complexes (I) 7 * 1 4 3 1 9 and thus throw more light not only on the influence of the steric and electronic nature of the amine nucleophile on reaction rates but also provide additional support on the predominance of large negative entropies of activation in the dissociative processes of lives. Each k o b s .…”

New Synthetic Routes to β‐Olefinic Triphenylphosphonium Salts via (Diolefin)tricarbonyliron Complexes

“…As we had previously extablished that neutral [(allyl)-Fe (CO)3X]-complexes also reacted with PPh3 to give free (2-en-1 -yl)phosphonium salts [6], an additional route to (E)-olefinic phosphonium salts was now available as evidenced by the formation of pure 3g, isomeric to 3a (Scheme 6). …”