Hang-gliding with Ferrocenes:  Unusual Coordination Chemistry of 1,1‘-Bis(mesitylthio)ferrocene

Abstract

A rare C,S-cyclometalated Pt IV complex is one of a series of transition metal complexes formed by the new redox-active and sterically hindered ligand 1,1′-bis-(mesitylthio)ferrocene. Simple Pd II and Pt II chelate species can be synthesized by less forcing reaction conditions, in addition to a Re 2 (CO) 6 Br 2 dinuclear species featuring the ferrocene ligand adopting a binucleating role and forming an unusual "quasi-closed" bridged structure.

New unsymmetrical thioether- and thiolate-substituted ferrocenediyl ligands and their metal complexes

“…It is interesting to compare the redox behaviour of the couple 2/4 with that of the related symmetric ligand 1,1Ј-bis(mesitylthio)ferrocene, 10, and its platinum complex 11 (Scheme 3). 8 As illustrated in Figs. 2c and d, in this case the separation between the one-electron oxidation of the platinum complex and that of the free ligand is about 0.6 V. This means that the symmetric ligand 10 exhibits a higher coordinating ability towards the PtCl 2 fragment than that of the asymmetric ligand 2.…”

“…The reactivity of 2 was investigated with platinum() and palladium() precursors and compared to analogous reactions involving 1,1Ј-(bismethylthio)ferrocene 7 and 1,1Ј-bis(mesitylthio)ferrocene. 8 A slight excess of the ligand was added to a toluene solution of bis(benzonitrile)dichlorometal() (where metal is Pt II or Pd II ) and the mixture heated to 60 ЊC. The yellow (for 4) and purple (for 5) solutions were heated at 60 ЊC for 20 h and hot filtered to remove any unreacted metal complex.…”

“…Notably different is the behaviour of the "hang-glider like" cyclometalated platinum complex 14. 8 The corresponding monocation [14] ϩ is quite long-lived indicating that hexacoordination renders the platinum complex stable in its oxidised form. The one-electron removal causes the original light yellow solution to turn light green, suggesting that the HOMO level is essentially iron centred.…”

1,1′-Di(heteroatom)-functionalised ferrocenes as [N,N], [O,O] and [S,S] chelate ligands in transition metal chemistry

“…25). 34 In the case of 42b (M 5 Pt), a cyclometalation reaction occurred upon prolonged heating in refluxing toluene solution, affording the hexacoordinate Pt IV complex 43.…”

Gold and silver complexes with the ligands Fc(SPh)2 and Fc(SePh)2 (Fc = (η5-C5H4)2Fe)

“…Several alkyl or aryl thio-or seleno-ferrocenes have been previously described; these are usually obtained by reaction of 1,1Ј-dilithioferrocene with the corresponding disulfide or diselenide, 5-7 although some unsymmetrically disubstituted derivatives have been prepared by cleavage of the trisulfur bridge in 1,2,3-trithia [3]ferrocenophane. 8, 9 The coordination chemistry of these ligands has been studied mainly with palladium and platinum; some silver complexes have been recently reported. 5-7,9, 10 As far as we are aware the only gold compounds described with ferrocenylthio derivatives have been recently reported by us, using the ligand 1,1bis(pyridylthio)ferrocene, 11 and no gold or silver compounds have been described with ferrocenylseleno derivatives.…”