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The iron(0) isocyanide derivatives Fe(CO) 2 [P(OPh) 3 ] 2 (CNR), where R = phenyl,  para -tolyl and mesityl, respectively, are obtained upon photolysis of Fe(CO) 3 [P(OPh) 3 ] 2  and reaction of the resulting photoproduct, HFe(CO) 2 [P(OPh) 3 ][(PhO) 2 P( o -OC 6 H 4 )], with CNR. All three molecular structures possess a similar trigonal bipyramidal geometry about the iron metal core, with  trans  apical phosphite ligands and a trigonal planar arrangement of CO and isocyanide ligands. The phenyl isocyanide complex crystallises with two molecules per asymmetric unit (in  P 2 1 / a ) comprising one ordered molecule with a bent isocyanide ligand C=N-C Ph  163.5(3)° and a second molecule which is disordered with two components of equal site occupancy. The  para -tolyl and mesityl isocyanide derivatives (both in  C 2/ c ) have two-fold crystallographic symmetry, with the iron atom and the isocyanide ligands residing on the two-fold axes.

Arylisocyanide derivatives of iron(0): crystal and molecular structures of Fe(CO) 2 [P(OPh) 3 ] 2 (CNR) (R = phenyl, para -tolyl, mesityl)