Reaction chemistry of 1,1′-ferrocene dicarboxylate towards M(ii) salts (M = Co, Ni, Cu): solid-state structure and electrochemical, electronic and magnetic properties of bi- and tetrametallic complexes and coordination polymers

Abstract

The synthesis and characterisation of a series of novel complexes of type [((tmeda)M-OC(O)-fc-(micro-CO(2)))(2)(micro-H(2)O)] (M = Co, ; M = Ni, ), zwitter-ionic [((pmdta)(H(2)O)Cu(+)-OC(O)-fc-CO(2)(-))(CH(3)OH)] (), and coordination polymer [(tmeda)Cu((OC(O))(2)fc)](n) () (fc = ferrocene-1,1'-diyl, (eta(5)-C(5)H(4))(2)Fe; tmeda = N,N,N',N'-tetramethylethylenediamine; pmdta = 1,1,4,7,7-N,N,N',N'',N''-pentamethyldiethylenetriamine) composed of ferrocene dicarboxylates and [(tmeda)/(pmdta)M](2+) entities is reported. These complexes could be prepared from [M(NO(3))(2)(tmeda)] (M = Co, ; M = Ni, ; M = Cu, ) and [Cu(NO(3))(2)(pmdta)] (), respectively, with stoichiometric amounts of 1,1'-ferrocene dicarboxylic acid () in presence of [n-Bu(4)N]OH-H(2)O. The molecular structures of , , , and in the solid state have been determined by single-crystal X-ray structure analysis. Electrochemical and UV-vis-NIR spectroscopic studies of these complexes are discussed in terms of electronic communication between the redox-active transition metals. In addition, the magnetic properties of and have been studied by susceptibility measurements vs. temperature. In complex , the two cobalt(ii) ions are antiferromagnetically coupled, while in the Ni-Ni coupling is ferromagnetic with J approximately +2.2(1) cm(-1).

Syntheses and structures of four copper(II) complexes constructed from m-ferrocenylbenzoate and N-donor ligands

“…The CueO bond distances are 1.941(5) and 2.669(6) Å, which are comparable to those in 1. The CueN bond distance is 1.987(7) Å, which is comparable to those in the similar copper(II) complexes [33,34]. The balk 2,2 0 -bpy ligand prevents the dimerization of two discrete m-ferrocenylbenzoate copper(II) complexes forming the discrete complex 2, which has been observed in the reported m-ferrocenylbenzoate metal complex [25].…”

Syntheses, structures, and electrochemical properties of four complexes based on 4-ferrocenylbutyrate ligand

“…Thus introducing ferrocenyl carboxylates into complexes and further exploiting the relationships between their structures and their properties have constituted one of the most attractive research fields in modern chemistry. Up to now, numerous complexes containing ferrocenyl carboxylates have been reported [13][14][15][16], whereas the complexes based on 4-ferrocenylbutyrate ligand are rarely reported [13]. Unlike other ferroceneyl carboxylates ligands, 4-ferrocenylbutyrate holds flexibility and can exhibit various conformations and different coordination modes when it coordinates to metal ions.…”

1,1′-Fc(4-C6H4CO2Et)2and its unusual salt derivative withZ′ = 5,catena-[Na+]2[1,1′-Fc(4-C6H4CO2−)2]·0.6H2O [1,1′-Fc = (η5-(C5H4)2Fe]

“…While (II) differs considerably from the metal-organic frameworks frequently encountered in transition metal chemistry (Tranchemontagne et al, 2009), it nonetheless contains features that encompass organometallic, organic, coordination and materials chemistry (Kü hnert et al, 2009) as well as hydrogen-bonding studies. The crystal structure of (II) may stimulate further studies encompassing these areas with a view to novel structures, spectroscopic and electrochemical applications.…”