Prganometallic sulfur complexes

Multifunctional iron thiocarboxylate complexes: synthesis, reactivity and structure of CpFe(CO)2SCO-3,5-C6H4(COCl)2

“…The 1 H-NMR spectra of (1)-(3) exhibit a singlet in the range of 5.03-5.09 ppm for the Cp-protons. This chemical shift range is similar to that observed for the thiocarboxylate (4.98-5.13 ppm) [9,10] and thiocarbonate (4.98-5.12 ppm) analogues [12]. The protons of the phenyl ring appear as two sets for (1) (doublet and triplet) and for (2) (two broad singlets) and as one singlet for (3).…”

“…Their i.r. spectra show 2 bands for the terminal carbonyl groups in of 2047-2044 and 2003-2000 cm -1 , which are comparable to those reported for the corresponding thiocarboxylates CpFe(CO) 2 SCOR[9,10]. The bands are shifted to lower wave-numbers as the number of the iron fragment increases, consistent with increasing electron density around the metal centre.…”

“…The structure of (1) is a typical piano stool with three legs in which the cyclopentadinyl ligand is bonded to iron in an g 5 -fashion. The Fe-C(Cp) (average = 2.093 Å ) and Fe-C(CO) (1.764(7), 1.786(6) Å ) bond lengths of (1) are similar to those found in CpFe(CO) 2 -containing complexes [8][9][10][11][12][13][14]. The Fe-S bond distance in (1) of 2.2529(14) Å is comparable to that found in CpFe(CO) 2 (7)).…”

“…Their reactions with mono-functional electrophiles such as acid chlorides [9,10], sulfonyl chlorides [11], chloroformates [12], chlorothioformates [13], chlorodithioformates [14], and O-alkyloxalyl chlorides [15] produced the complexes CpFe(CO) 2 SZ (Z = COR, SO 2 R, CO 2 R, C(S)OR, CS 2 R, COCO 2 R) which contain one iron centre. The reaction of these iron sulfides with bifunctional acid chlorides, such as oxalyl chloride, gave [CpFe (CO) 2 SCO] 2 which contains two iron atoms [15].…”

Synthesis and biological study of a new series of bifunctional organoiron thio‐ and seleno‐terephthalate derivatives (C5H5)Fe(CO)2ECO(C6H4)COX (E = S, X = R2N, RNH, NH2, OH, Cl; E = Se, X = RNH, RS, RCOO, NH2, OH, Cl)

“…26 There are two very strong bands in the ranges 2010±2060 and 1960± 2000 cm À1 , corresponding to the stretching frequencies of the two terminal carbonyl groups bonded to the iron center. The strong band in the range 1580±1600 cm À1 is assigned to the thiocarboxylate part (SC=O) 29 and that in the range 1600±…”