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Variable coordination of redox-active TCNB in discrete and polymeric ferrocenylcopper(i) complexes: Structures and spectroelectrochemical behaviour
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SYSNO ASEP 0421149 Document Type J - Journal Article R&D Document Type Journal Article Subsidiary J Článek ve WOS Title Variable coordination of redox-active TCNB in discrete and polymeric ferrocenylcopper(i) complexes: Structures and spectroelectrochemical behaviour Author(s) Jana, R. (DE)
Mobin, S. M. (IN)
Schwederski, B. (DE)
Fiedler, Jan (UFCH-W) RID, ORCID
Kaim, W. (DE)Source Title Dalton Transactions. - : Royal Society of Chemistry - ISSN 1477-9226
Roč. 42, č. 45 (2013), s. 16142-16150Number of pages 9 s. Language eng - English Country GB - United Kingdom Keywords Bis(diphenylphosphino) ferrocene ; Coordination Polymers ; Discrete transitions Subject RIV CF - Physical ; Theoretical Chemistry R&D Projects GA203/09/0705 GA ČR - Czech Science Foundation (CSF) Institutional support UFCH-W - RVO:61388955 UT WOS 000326782600047 EID SCOPUS 84886805922 DOI 10.1039/c3dt51360b Annotation 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. Workplace J. Heyrovsky Institute of Physical Chemistry Contact Michaela Knapová, michaela.knapova@jh-inst.cas.cz, Tel.: 266 053 196 Year of Publishing 2014
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