Piesch Martin, Graßl Christian, Scheer Manfred
Institut für Anorganische Chemie, Universität Regensburg, 93040, Regensburg, Germany.
Angew Chem Int Ed Engl. 2020 Apr 27;59(18):7154-7160. doi: 10.1002/anie.201916622. Epub 2020 Mar 13.
The redox chemistry of [(Cp'''Co) (μ,η :η -E ) ] (E=P (1), As (2); Cp'''=1,2,4-tri(tert-butyl)cyclopentadienyl) was investigated. Both compounds can be oxidized and reduced twice. That way, the monocations [(Cp'''Co) (μ,η :η -E )][X] (E=P, X=BF (3 a), [FAl] (3 b); E=As, X=BF (4 a), [FAl] (4 b)), the dications [(Cp'''Co) (μ,η :η -E )][TEF] (E=P (5), As (6)), and the monoanions [K(18-c-6)(dme) ][(Cp'''Co) (μ,η :η -E )] (E=P (7), As (8)) were isolated. Further reduction of 7 leads to the dianionic complex [K(18-c-6)(dme) ][K(18-c-6)][(Cp'''Co) (μ,η :η -P )] (9), in which the cyclo-P ligand has rearranged to a chain-like P ligand. Further reduction of 8 can be achieved with an excess of potassium under the formation of [K(dme) ][(Cp'''Co) (μ,η :η -As )] (10) and the elimination of an As unit. Compound 10 represents the first example of an allylic As ligand incorporated into a triple-decker complex.
研究了[(Cp'''Co)(μ,η²:η² - E)]（E = P (1)，As (2)；Cp''' = 1,2,4 - 三(叔丁基)环戊二烯基）的氧化还原化学。这两种化合物都可以进行两次氧化和还原。通过这种方式，分离得到了单核阳离子[(Cp'''Co)(μ,η²:η² - E)][X]（E = P，X = BF₄ (3a)，[FAl] (3b)；E = As，X = BF₄ (4a)，[FAl] (4b)）、双核阳离子[(Cp'''Co)(μ,η²:η² - E)][TEF]（E = P (5)，As (6)）以及单阴离子[K(18 - c - 6)(dme)][(Cp'''Co)(μ,η²:η² - E)]（E = P (7)，As (8)）。7的进一步还原生成了二阴离子配合物[K(18 - c - 6)(dme)][K(18 - c - 6)][(Cp'''Co)(μ,η²:η² - P)] (9)，其中环 - P配体重排为链状P配体。在形成[K(dme)][(Cp'''Co)(μ,η²:η² - As)] (10)并消除一个As单元的情况下，用过量的钾可以实现8的进一步还原。化合物10代表了一个烯丙基As配体并入三层夹心配合物的首例。
