Synthesis and Electrochemical Reactivity of sigma-Bonded and N-Substituted Cobalt Porphycenes.
Synthesis and Electrochemical Reactivity of sigma-Bonded and N-Substituted Cobalt Porphycenes.
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西格玛键合和N-取代的钴卟啉的合成和电化学反应性。
DOI：
10.1021/ic971534c
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发表时间：
1998
影响因子：
4.6
通讯作者：
R. Guilard
中科院分区：
文献类型：
--
作者：
K. Kadish;P. Boulas;M. Kisters;E. Vogel;A. Aukauloo;F. D’Souza;R. Guilard
报道了σ键合且N - 取代的钴卟吩的首次合成与表征。所研究的化合物表示为(Pc)Co(R)和(N - CH₃OEPc)CoCl，其中R为CH₃或C₆H₅，Pc是2,3,6,7,12,13,16,17 - 八乙基卟吩（OEPc）、2,7,12,17 - 四丙基卟吩（TPrPc）或2,7,12,17 - 四乙基 - 3,6,13,16 - 四甲基卟吩（EtioPc）的二价阴离子，N - CH₃OEPc是N - 甲基 - 2,3,6,7,12,13,16,17 - 八乙基卟吩的一价阴离子。每种σ键合的(Pc)Co(R)衍生物都能可逆地被两个电子还原或氧化，但在[(Pc)Co(R)]⁺⁽⁺⁾⁽⁺⁾电生成之后，σ键合的R基团会发生缓慢迁移，最终产物是一种N - 取代的钴(II)卟吩，它也具有电活性，在乙腈中会发生两次还原。该反应的单还原产物被表述为一个Co(II) π - 阴离子自由基，它会发生CH₃基团的缓慢“回迁”，重新生成(OEPc)Co(CH₃)。
The first synthesis and characterization of sigma-bonded and N-substituted cobalt porphycenes is reported. The investigated compounds are represented as (Pc)Co(R) and (N-CH(3)OEPc)CoCl, where R is CH(3) or C(6)H(5), Pc is the dianion of 2,3,6,7,12,13,16,17-octaethylporphycene (OEPc), 2,7,12,17-tetrapropylporphycene (TPrPc), or 2,7,12,17-tetraethyl-3,6,13,16-tetramethylporphycene (EtioPc), N-CH(3)OEPc is the monoanion of N-methyl-2,3,6,7,12,13,16,17-octaethylporphycene. Each sigma-bonded (Pc)Co(R) derivative can be reversibly reduced or oxidized by two electrons, but a slow migration of the sigma-bonded R group occurs following electrogeneration of [(Pc)Co(R)](+)()(*)() leading, as a final product, to an N-substituted cobalt(II) porphycene which is also electroactive and undergoes two reductions in PhCN. The singly reduced product of this reaction is formulated as a Co(II) pi-anion radical which undergoes a slow "back-migration" of the CH(3) group to regenerate (OEPc)Co(CH(3)).