Abstract
Herein is reported the structural characterization and scalable preparation of the elusive iron-phosphido complex FpP( (t) Bu)(F) (2-F, Fp = (Fe(η(5)-C(5)H(5))(CO)(2))) and its precursor FpP( (t) Bu)(Cl) (2-Cl) in 51% and 71% yields, respectively. These phosphide complexes are proposed to be relevant to an organoiron catalytic cycle for phosphinidene transfer to electron-deficient alkenes. Examination of their properties led to the discovery of a more efficient catalytic system involving the simple, commercially available organoiron catalyst Fp(2). This improved catalysis also enabled the preparation of new phosphiranes with high yields ( (t) BuPCH(2)CHR; R = CO(2)Me, 41%; R = CN, 83%; R = 4-biphenyl, 73%; R = SO(2)Ph, 71%; R = POPh(2), 70%; R = 4-pyridyl, 82%; R = 2-pyridyl, 67%; R = PPh(3) (+), 64%) and good diastereoselectivity, demonstrating the feasibility of the phosphinidene group-transfer strategy in synthetic chemistry. Experimental and theoretical studies suggest that the original catalysis involves 2-X as the nucleophile, while for the new Fp(2)-catalyzed reaction they implicate a diiron-phosphido complex Fp(2)(P (t) Bu), 4, as the nucleophile which attacks the electron-deficient olefin in the key first P-C bond-forming step. In both systems, the initial nucleophilic attack may be accompanied by favorable five-membered ring formation involving a carbonyl ligand, a (reversible) pathway competitive with formation of the three-membered ring found in the phosphirane product. A novel radical mechanism is suggested for the new Fp(2)-catalyzed system.