%0 Journal Article %1 Jana.2013b %A Jana, Rajkumar %A Mobin, Shaik M. %A Schwederski, Brigitte %A Fiedler, Jan %A Kaim, Wolfgang. %D 2013 %J Dalton Transactions %K copper crystal macrocycle mol phosphinoferrocene prepn spectroelectrochem structure tetracyanobenzene %N 45 %P 16142--16150 %R 10.1039/c3dt51360b %T Variable coordination of redox-active TCNB in discrete and polymeric ferrocenylcopper(i) complexes: Structures and spectroelectrochemical behaviour %V 42 %X 1,2,4,5-Tetracyanobenzene (TCNB) was reacted with Cu(dppf)(CH3CN)2(BF4) and Cu(dchpf)(CH3CN)(BF4), dppf = 1,1'-bis(diphenylphosphino)ferrocene and dchpf = 1,1'-bis(dicyclohexylphosphino)ferrocene, to produce a heterotetranuclear metallamacrocycle 1, Cu(dppf)(μ-TCNB)(BF4)2, and a heterooctanuclear complex 2, Cu(dchpf)4(m4-TCNB)(BF4)4. Complex 1 is the first example of a structurally characterized discrete transition metal complex of TCNB. Upon crystn. attempts, compd. 2 formed the structurally identified coordination polymer 3, Cu(dchpf)(μ-TCNB)2(BF4)2n. Structural and spectroscopic analyses confirmed the redox-innocent behavior of TCNB in 1, 2 and 3. However, the sol. compds. 1 and 2 could be oxidized and reduced spectroelectrochem. (UV-vis, IR, and EPR). The oxidn. occurs invariably at the ferrocene sites without notable splitting of redox potentials. Redn. involves the TCNB bridging ligands to produce radical complexes. As a variably bridging acceptor component of supramol. 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. on SciFinder(R)

@article{Jana.2013b, abstract = {1,2,4,5-Tetracyanobenzene (TCNB) was reacted with [Cu(dppf)(CH3CN)2](BF4) and [Cu(dchpf)(CH3CN)](BF4), dppf = 1,1'-bis(diphenylphosphino)ferrocene and dchpf = 1,1'-bis(dicyclohexylphosphino)ferrocene, to produce a heterotetranuclear metallamacrocycle 1, {[Cu(dppf)(μ-TCNB)](BF4)}2, and a heterooctanuclear complex 2, [{Cu(dchpf)}4(\textgreek{m}4-TCNB)](BF4)4. Complex 1 is the first example of a structurally characterized discrete transition metal complex of TCNB. Upon crystn. attempts, compd. 2 formed the structurally identified coordination polymer 3, {[Cu(dchpf)(μ-TCNB)]2(BF4)2}n. Structural and spectroscopic analyses confirmed the redox-innocent behavior of TCNB in 1, 2 and 3. However, the sol. compds. 1 and 2 could be oxidized and reduced spectroelectrochem. (UV-vis, IR, and EPR). The oxidn. occurs invariably at the ferrocene sites without notable splitting of redox potentials. Redn. involves the TCNB bridging ligands to produce radical complexes. As a variably bridging acceptor component of supramol. 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. [on SciFinder(R)]}, added-at = {2022-06-15T11:26:56.000+0200}, author = {Jana, Rajkumar and Mobin, Shaik M. and Schwederski, Brigitte and Fiedler, Jan and Kaim, Wolfgang.}, biburl = {https://puma.ub.uni-stuttgart.de/bibtex/252097f6c30a5ac7cebaf1744e5b23dc7/huebleriac}, doi = {10.1039/c3dt51360b}, interhash = {f52379a27dbfef3c3fe7119c05482419}, intrahash = {52097f6c30a5ac7cebaf1744e5b23dc7}, issn = {1477-9226}, journal = {Dalton Transactions}, keywords = {copper crystal macrocycle mol phosphinoferrocene prepn spectroelectrochem structure tetracyanobenzene}, number = 45, pages = {16142--16150}, timestamp = {2022-06-15T09:26:56.000+0200}, title = {Variable coordination of redox-active TCNB in discrete and polymeric ferrocenylcopper(i) complexes: Structures and spectroelectrochemical behaviour}, volume = 42, year = 2013 }