Abstract
The synthesis of the metastable triple-decker complex [(Cp*Fe)(Cp'''Co)(mu,eta(5):eta(4)-As-5)] (3) (Cp* = pentamethyl-cyclopentadienyl, Cp''' = 1,2,4-tritertbutyl-cyclopentadienyl) is reported. 3 is sensitive toward thermal activation (and in solutions of acetonitrile), which converts 3 selectively into [(Cp*Fe)(Cp'''Co)(mu,eta(3):eta(3)-As-3)] (4) and [(Cp*Fe)(2)(Cp'''Co)(2) ...
Abstract
The synthesis of the metastable triple-decker complex [(Cp*Fe)(Cp'''Co)(mu,eta(5):eta(4)-As-5)] (3) (Cp* = pentamethyl-cyclopentadienyl, Cp''' = 1,2,4-tritertbutyl-cyclopentadienyl) is reported. 3 is sensitive toward thermal activation (and in solutions of acetonitrile), which converts 3 selectively into [(Cp*Fe)(Cp'''Co)(mu,eta(3):eta(3)-As-3)] (4) and [(Cp*Fe)(2)(Cp'''Co)(2) (mu(4),eta(4):eta(4):eta(4):eta(3)-As-11)] (5). Harsher thermal reaction conditions lead to a further fragmentation into [Cp*Fe(eta(5)-As-5)] (1b), [(Cp'''Co)(2)(mu,eta(2):eta(2)-As-2)(2)] (6), and [(Cp*Fe)(2)(Cp'''Co)(mu(3),eta(2):eta(2):eta(2)-As-3)(2)] (7), which can be completed by longer reaction times or higher temperatures. The fragmentation was investigated by variable-temperature and time-dependent NMR spectroscopy, and a fine-tuning of the selectivity can be achieved by applying different reaction conditions. All compounds were fully characterized, and their electronic structures were elucidated by DFT calculations.
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