Half sandwich iron S-bonded mono-thiocarbonate complexes: structure of CpFe(CO)2SCO2Et

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

“…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].…”

Reactivity of U–E–U (E = S, Se) Toward CO2, CS2, and COS: New Mixed-Carbonate Complexes of the Types U–CO2E–U (E = S, Se), U–CS2E–U (E = O, Se), and U–COSSe–U

“…The two C–O distances in 2 , measuring 1.283(5) and 1.262(5) Å, are suggestive of electron delocalization and further confirm the coordination of a dianionic CO 2 S 2– ligand. Similarly, the C–Se distance in 4 of 1.925(7) Å is comparable to that of monoanionic alkyl selenocarbonate complex [CpFe(CO) 2 SeCO 2 Et] [1.914(4) Å], and the nearly equivalent C–O distances in 4 are also attributed to electron delocalization of a coordinating dianionic CO 2 Se 2– ligand.…”

“…The U–Se and C–Se distances in 4 of 3.0122(10) and 1.925(7) Å are significantly longer than the U–S and C–S distances in 2 of 2.892(1) and 1.742(5) Å, in accordance with a larger and softer selenium atom compared to sulfur. The C–S distance [1.742(5) Å] in 2 is comparable to monoanionic alkyl thiocarbonate complexes [CpFe(CO) 2 SCO 2 Et] [1.748(3) Å] and [ fac -(CO) 3 (dppe)MnSC(O)OCH 3 ] [1.729(10) Å]. The distinguishing feature is in the C–O distances, where for [CpFe(CO) 2 SCO 2 Et] and [ fac -(CO) 3 (dppe)Mn(SC(O)OCH 3 )] the C–O distance is closer to a double bond [1.197(3) and 1.200(11) Å, respectively] and the C–OR bonds are long, 1.346(4) and 1.354(10) Å, respectively.…”

“…The C–S distance [1.742(5) Å] in 2 is comparable to monoanionic alkyl thiocarbonate complexes [CpFe(CO) 2 SCO 2 Et] [1.748(3) Å] and [ fac -(CO) 3 (dppe)MnSC(O)OCH 3 ] [1.729(10) Å]. The distinguishing feature is in the C–O distances, where for [CpFe(CO) 2 SCO 2 Et] and [ fac -(CO) 3 (dppe)Mn(SC(O)OCH 3 )] the C–O distance is closer to a double bond [1.197(3) and 1.200(11) Å, respectively] and the C–OR bonds are long, 1.346(4) and 1.354(10) Å, respectively. The two C–O distances in 2 , measuring 1.283(5) and 1.262(5) Å, are suggestive of electron delocalization and further confirm the coordination of a dianionic CO 2 S 2– ligand.…”