78782-43-1Relevant articles and documents
(Cross-conjugated dienyl)tricarbonyliron cations. 4. Trimethyl derivatives
Bonazza, Benedict R.,Peter Lillya,Scholes, Gary
, p. 137 - 142 (2008/10/08)
Isomeric [trimethyl(cross-conjugated dienyl)]tricarbonyliron cations A (lia) and B (lib) have been generated in SO2 at -65 °C by using 2-3 equiv of FSO3H or excess PSO3H and excess 1:1 SbF5/FSO3H. Precursors 3-5 all produce the same equilibrium A/B mixture. These observations, and the isomerization which attends generation of A and B from 3 followed by immediate methonolysis at low temperature to give mainly 5, require facile isomerization about the C2-C3 bond at low temperature. At temperatures up to -40 °C no NMR line broadening owing to rotation is observed. Warming of the A/B mixture to -50 °C causes conversion to a σπ-allyl complex of structure 7a or 7b. Generation of the cations under short lifetime conditions by solvolysis in 80% aqueous acetone gives nearly complete (95%) isomerization. Cations A and B fail to give detectable fluorosulfonate, halide, or CO adducts, possibly owing to an increase in steric crowding attendant to adduct formation. Isomerization to the (conjugated dienyl)tricarbonyliron cation 10 resulted when 3 was treated with HBF4 under 1 atm of CO at 0 °C. These observations are in accord with our earlier deduction that (cross-conjugated dienyl)tricarbonyliron cations do not possess the coordinatively unsaturated structure 1 predicted by a one-interaction frontier orbital model but that they can achieve such a structure at the cost of a modest amount of energy.