Reactions of (η-benzylideneacetone)Fe(CO) and the α,ω-diphosphines ArP(CH)PAr afford the trigonal bipyramidal diiron tetraphosphorus complexes ,-(CO)Fe[ArP(CH)PAr]Fe(CO) (/Ar = 3/Ph , 4/Ph , 4/-tol ; 56-19%). Crystal structures establish essentially parallel P-Fe-P axes, iron-iron distances of 5.894(9)-5.782(1) Å () and 6.403(1)-6.466(1) Å (,), and van der Waals radii of 4.45 Å for the Fe(CO) rotators, the planes of which are offset by 0.029-1.665 Å. Analogous reactions of PhP(CH)PPh yield the square pyramidal monoiron complex -(CO)Fe[PhP(CH)PPh] (, 31%), a rare case where a diphosphine spans basal positions (∠P-Fe-P 147.4(2)°). Both and exhibit two CO C NMR signals at room temperature, indicating slow exchange on the NMR time scale, which in the former could entail Fe(CO)/Fe(CO) gearing. Under analogous conditions, , exhibit one signal. Previously reported adducts of Fe(CO) and PhP(CH)PPh are surveyed (1:1, = 1-5; 2:2, = 5), and the IR ν band patterns and energies of all complexes analyzed with the aid of DFT calculations. The diiron complexes are preferred thermodynamically. Attention is given to limiting types of Fe(CO)/Fe(CO) interactions in the diiron complexes.
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