Variable coordination of redox-active TCNB in discrete and polymeric ferrocenylcopper(i) complexes: Structures and spectroelectrochemical behaviour

0421149 - ÚFCH JH 2014 RIV GB eng J - Článek v odborném periodiku
Jana, R. - Mobin, S. M. - Schwederski, B. - Fiedler, Jan - Kaim, W.
Variable coordination of redox-active TCNB in discrete and polymeric ferrocenylcopper(i) complexes: Structures and spectroelectrochemical behaviour.
Dalton Transactions. Roč. 42, č. 45 (2013), s. 16142-16150. ISSN 1477-9226. E-ISSN 1477-9234
Grant CEP: GA ČR GA203/09/0705
Institucionální podpora: RVO:61388955
Klíčová slova: Bis(diphenylphosphino) ferrocene * Coordination Polymers * Discrete transitions
Kód oboru RIV: CF - Fyzikální chemie a teoretická chemie
Impakt faktor: 4.097, rok: 2013

1,2,4,5-Tetracyanobenzene (TCNB) was reacted with [Cu(dppf)(CH 3CN)2](BF4) and [Cu(dchpf)(CH 3CN)](BF4), dppf = 1,1′-bis(diphenylphosphino) ferrocene and dchpf = 1,1′-bis(dicyclohexylphosphino)ferrocene, to produce a heterotetranuclear metallamacrocycle 1, {[Cu(dppf)(μ-TCNB)](BF 4)}2, and a heterooctanuclear complex 2, [{Cu(dchpf)} 4(μ4-TCNB)](BF4)4. Complex 1 is the first example of a structurally characterised discrete transition metal complex of TCNB. Upon crystallisation attempts, compound 2 formed the structurally identified coordination polymer 3, {[Cu(dchpf)(μ-TCNB)] 2(BF4)2}n. Structural and spectroscopic analyses confirmed the redox-innocent behaviour of TCNB in 1, 2 and 3. However, the soluble compounds 1 and 2 could be oxidised and reduced spectroelectrochemically (UV-vis, IR, and EPR). The oxidation occurs invariably at the ferrocene sites without notable splitting of redox potentials. Reduction involves the TCNB bridging ligands to produce radical complexes. As a variably bridging acceptor component of supramolecular structures the TCNB ligand thus adopts an intermediate position between the highly electron transfer-active TCNE, TCNQ and TCNQF4 systems and the numerous redox-innocent bridges.
Trvalý link: http://hdl.handle.net/11104/0227631