Reaction of [Fe2(μ-CS)(μ-CSMe)Cp2(CO)2]+ (1) with sodium N,N-dimethyldithiocarbamate [Me2dtc]Na affords a mixture of the dithiocarbene [FeFe(μ-CS){μ-C(SMe)SC(S)NMe2}Cp(CO)] (2) and the thiocarbyne [Fe2(μ-CS)(μ-CSMe)(μ-S2CNMe2)Cp2] (3). Complex 2 is quantitatively converted into 3 by photochemical irradiation. The X-ray molecular structure of 3 demonstrates the presence of three bridging ligands and exhibits the shortest Fe-Fe interaction found in similar systems [2.453(1) Å]. Complex 3 can also be obtained by reacting [Me2dtc]- with the di-solvento thiocarbyne [Fe2(μ-CS)(μ-CSMe)(NCMe)2Cp2]+ (1a). By contrast no stable addition product has been isolated in analogous reactions involving the thiocarbyne [Fe2(μ-CO)(μ-CSMe)Cp2(CO)2]+ (1b). The [Me2dtc]- nucleophilic addition at the μ-C to form [Fe2(μ-CO){μ-C(CN)SC(S)NMe2}Cp2(CO)2] (4a) is obtained starting from [Fe2(μ-CO){μ-C(CN)(SMe2)}Cp2(CO)2]SO3CF3 (1d). Photochemical reaction of the cyanocarbene 4a causes intramolecular ring closure affording [FeFe(μ-CO){μ-C(CN)SC(S)NMe2}Cp2(CO)] (5a). © 2002 Elsevier Science B.V. All rights reserved.
Albano V.G., Bordoni S., Busetto L., Palazzi A., Sabatino P., Zanotti V. (2002). Dithiocarbamate derivatives of μ-thiocarbyne complexes: Synthesis and X-ray molecular structure of [Fe2(μ-CS)(μ-CSMe) (μ-S2CNMe2)Cp2]. JOURNAL OF ORGANOMETALLIC CHEMISTRY, 659(1-2), 15-21 [10.1016/S0022-328X(02)01652-2].
Dithiocarbamate derivatives of μ-thiocarbyne complexes: Synthesis and X-ray molecular structure of [Fe2(μ-CS)(μ-CSMe) (μ-S2CNMe2)Cp2]
Bordoni S.;
2002
Abstract
Reaction of [Fe2(μ-CS)(μ-CSMe)Cp2(CO)2]+ (1) with sodium N,N-dimethyldithiocarbamate [Me2dtc]Na affords a mixture of the dithiocarbene [FeFe(μ-CS){μ-C(SMe)SC(S)NMe2}Cp(CO)] (2) and the thiocarbyne [Fe2(μ-CS)(μ-CSMe)(μ-S2CNMe2)Cp2] (3). Complex 2 is quantitatively converted into 3 by photochemical irradiation. The X-ray molecular structure of 3 demonstrates the presence of three bridging ligands and exhibits the shortest Fe-Fe interaction found in similar systems [2.453(1) Å]. Complex 3 can also be obtained by reacting [Me2dtc]- with the di-solvento thiocarbyne [Fe2(μ-CS)(μ-CSMe)(NCMe)2Cp2]+ (1a). By contrast no stable addition product has been isolated in analogous reactions involving the thiocarbyne [Fe2(μ-CO)(μ-CSMe)Cp2(CO)2]+ (1b). The [Me2dtc]- nucleophilic addition at the μ-C to form [Fe2(μ-CO){μ-C(CN)SC(S)NMe2}Cp2(CO)2] (4a) is obtained starting from [Fe2(μ-CO){μ-C(CN)(SMe2)}Cp2(CO)2]SO3CF3 (1d). Photochemical reaction of the cyanocarbene 4a causes intramolecular ring closure affording [FeFe(μ-CO){μ-C(CN)SC(S)NMe2}Cp2(CO)] (5a). © 2002 Elsevier Science B.V. All rights reserved.I documenti in IRIS sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.
