Complexes 7ak−an, 7bk,bm [(R1NC(R2)−C(R3)O)Fe(CO)2PR3
a: R1 = tBu, R2 = H,
R3 = Ph; b: R1 = Me, R2 = Ph, R3 = Ph; k: R = OMe; l: R = Ph; m: R = Et; n: R = nPr],
and 7ao,bo [(R1NC(R2)−C(R3)O)Fe(CO)Ph2PCH2CH2PPh2] have been prepared by
substitution of CO in the respective tricarbonyl complexes 1a,b at room temperature. Various
dynamic processes have been investigated by 13C and 31P NMR. On the IR time scale, complex
7bk exists in two distinct isomeric forms. Complexes 7 have been characterized by IR, UV−vis, and 1H, 13C, and 31P NMR spectroscopy. Surprisingly, in the 1,3-dipolar cycloaddition
reaction of complexes 7 with the dipolarophiles dimethyl acetylenedicarboxylate (DMAD,
v), methyl propynoate (w), phenyl acetylene (x), and p-methoxyphenyl-isothiocyanate (y)
the bicyclic ferra[2.2.1] complexes 8, i.e., the initial cycloadducts, are stable and isolable.
With dimethyl maleate (z) it is formed reversibly. Complexes 8 containing one phosphorus
ligand are formed as two non-interconverting isomers. The molecular structure of 8aov,
C45H45FeNO6P2, has been determined by single-crystal X-ray diffraction. In pentane, the
initial cycloadduct (8bv) of the tricarbonyl 1b with DMAD is insoluble and precipitates. In
solution above −30 °C 8bv reacts further by insertion of CO into the Fe−O bond to the
Fe(CO)3(butenolide) complex 10bv. No intermediates can be detected by 1H, 13C, and IR
monitoring. The other complexes 8 do not insert CO and slowly decompose on stirring at
room temperature in THF. From the decomposition of complexes 8 with α-iminoketone a,
the organic compound 11a can be isolated. The cycloaddition reaction of 1a with DMAD (v)
in the presence of PR3 (k: R = OMe; l: R = Ph) results without detectable intermediates in
the formation of the Fe(CO)2PR3(butenolide) complexes 10akv,alv. They are formed as three
and two non-interconverting isomers, respectively. Reaction of 8bv with PEt3 also results
in the formation of the butenolide complex 10bmv; however, here the PEt3 ligand occupies
exclusively one of the equatorial positions. An explanation for the isomeric ratios of complexes
8 and 10 is discussed.