Photolytic CO-substitution reaction of organoiron thiocarboxylate derivatives CpFe(CO)2SCOR (R = alkyl, aryl) with diphosphines (Ph2P(CH2)nPPh2) (n=1-6):: X-ray crystal structure of [CpFe(dppm)SCO(3,5-(NO2)2C6H3)]

The photolytic CO-substitution reaction of the organoiron thiocarboxylate complexes CpFe(CO)(2)SCOR (R = CH(3), 2-CH(3)C(6)H(4) 2-NO(2)C(6)H(4), 4-NO(2)C(6)H(4), 3,5-(NO(2))(2)C(6)H(3)) with diphosphines (Ph(2)P(CH(2))(n)PPh(2)) [n = 1 (dppm), n = 2 (dppe), n = 3 (dpppr), n = 4 (dppb), n = 5 (dppp), n = 6 (dpph)] at room temperature using 1:2 (metal-ligand) molar ratio afforded exclusively the disubstituted complexes CpFe(Ph(2)P(CH(2))(n) PPh(2))SCOR when n = 1, 2 and 3 and the monosubstituted analogs CpFe(CO)(Ph(2)P(CH(2))(n) PPh(2))SCOR when n = 4, 5 and 6. This reaction was found to be strongly influenced by the backbone length of the diphosphine ligand, the nature of the R group of the thiocarboxylate moiety and the metal-ligand molar ratios. The crystal structure of CpFe(dppm)SCO(3,5-(NO(2))(2)C(6)H(3)) was determined. (C) 2002 Elsevier Science B.V. All rights reserved.