40459-94-7Relevant academic research and scientific papers
Charge-transfer salts of ferrocene derivatives with bis(maleonitriledithiolato)metallate(III) complexes ([M(mnt)2]-, M = Ni, Pt): A ground-state high-spin [(Ni(mnt)2)2]2- dimer
Zuercher, Stefan,Petrig, Jeannine,Perseghini, Mauro,Gramlich, Volker,Woerle, Michael,Von Arx, Dieter,Togni, Antonio
, p. 1324 - 1359 (1999)
New hexamethylated ferrocene derivatives containing thioether moieties (1,1'-bis[(tert-butyl)thio]-2,2',3,3',4,4'-hexamethylferrocene (3a,b)) or fused S-heteropolycyclic substituents (rac-1-[(1,3-benzodithiol-2- yliden)methyl]-2,2',3,3',4,4'-hexamethylferrocene (5) and rac-1-[1,2-bis(1,3- benzodithiol-2-yliden)ethyl]2,2',3,3',4,4'-hexamethylferrocene (14)), as well as a series of ferrocene-substituted vinylogous tetrathiafulvalenes (1,1'- bis[1,2-bis(1,3-benzodithiol-2-yliden)ethyl]ferrocene (6a), 1,1'-bis[1-(1,3- benzodithiol-2-yliden)-2(5,6-dihydro-1,3-dithiolo[4,5-b][1,4]dithiin-2- yliden)ethyl]ferrocene (6b), [1,2-bis(1,3-benzodithiol-2- yliden)ethyl]ferrocene (21a), [1-(1,3-benzodithiol-2-yliden)-2-(5,6-dihydro- 1,3-dithiolo[4,5-b][1,4]dithiin-2-yliden)ethyl]ferrocene (21b), [1,2-bis(5,6- dihydro-1,3-dithiolo[4,5-b][1,4]dithiin-2-yliden)ethyl]ferrocene (21c), [1(5,6-dihydro-1,3-dithiolo[4,5-b][1,4]dithiin-2-yliden)-2-(1,3-benzodithiol- 2-yliden)ethyl]ferrocene (21d)) were prepared and fully characterized. Their redox properties show that some of them are easily oxidized and undergo transformation to paramagnetic salts containing bis(maleonitriledithiolato)- metallate(III) anions [M(mnt)2]- (M=Ni, Pt; bis[2,3-dimercapto-κS)but-2- enedinitrilato(2-)]nickelate (1-) or -platinate (1-). The derivatives [3a][Ni(mnt)2] (26), [3a][Pt(mnt)2] (27), [Fe{(n5- C5Me4S)2S}][Ni(Mnt)2] (28), [Fe{(n5c5Me4s)2S}[Pt(mnt)2] (29), [5] [Ni(mnt)2]·ClCH2CH2Cl (30), [6a] [Ni(mnt)2] (31), [6a] [Ni(mnt)2]. CICH2CH2Cl (31a), [6a] [Pt(mnt)2] [32), and [6b] [Ni(mnt)2] (33) were prepared and fully characterized, including by SQUID (superconducting quantum interference device) susceptibility measurements. X-Ray crystal-structural studies of the neutral ferrocene derivatives 6a,b, 21c,d, and 1,1'-bis[1- (1,3-benzodithiol-2-yliden)-2-oxoethyl]ferrocene (23), as well as of the charge-transfer salts 26-28, 30, and 31a, are reported. The salts 28 and 30 display both a D+A-A-D+ structural motif, however, with a different relative arrangement of the [{Ni(mnt)2}2]2- dimers, thus giving rise to different but strong antiferromagnetic couplings. Salt 26 exhibits isolated ferromagnetically coupled [{Ni(mnt)2}2]2- dimers. Salt 27 displays a D+A-D+A- structural motif in all three space dimensions, and a week ferromagnetic ordering at low temperature. Salt 31a, on the contrary, shows segregated stacks of cations and anions. The cations are connected with each other in two dimensions, and the anions are separated by a 1,2-dichloroethane molecule.
