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Fe(CO) 5  reacts with [PPh 2 ] -  in THF at -78 °C to give the adduct [(CO) 4 FeCOPPh 2 ] -  (3) which decomposes at elevated temperature to give [(CO) 4 FePPh 2 ] -  (1), [Fe 2 (CO) 8 ] 2-  (2) and (Ph 2 P) 2  probably via a radical mechanism. Attempts to transfer 3 with the electrophiles MeSO 3 CF 3  or Me 3 SnCl into the corresponding carbenes have failed and Fe(CO) 5  along with Ph 2 PMe and Me 3 SnPPh 2 , respectively, are formed. 1 adds one equivalent of CS 2  to generate [(CO) 4 FePPh 2 CS 2 ] -  (4). The [K-18-Krone-6] salt of 1 crystallizes in the triclinic space group P 1̄ with the unit cell parameters a = 929.5(2), b = 1112 .1(2), c = 2017.9(4) pm, α = 100.29(3)°; β = 94.07(3) °; γ = 114.58(3) °. The existence of 3 is established by low temperature  31 P NMR spectroscopy.

zeitschrift für naturforschung b

Über die Reaktion von KPPh 2  mit Fe(CO) 5  und Fe(CO) 4 CS; Molekülstruktur von [(CO) 4 FePPh 2 ] -  / On the Reaction of KPPh*, with Fe(CO) 5  and Fe(CO) 4 CS; Molecular Structure of [(CO) 4 FePPh 2 ] -