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Synthesis of a Heterobimetallic Arsenic Triple-Decker Complex and Its Fragmentation Chemistry
dataset
posted on 2020-05-22, 20:29 authored by Martin Piesch, Manfred ScheerThe
synthesis of the metastable triple-decker complex [(Cp*Fe)(Cp‴Co)(μ,η5:η4-As5)] (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)(μ,η3:η3-As3)] (4) and [(Cp*Fe)2(Cp‴Co)2 (μ4,η4:η4:η4:η3-As11)] (5). Harsher thermal reaction conditions
lead to a further fragmentation into [Cp*Fe(η5-As5)] (1b), [(Cp‴Co)2(μ,η2:η2-As2)2] (6), and [(Cp*Fe)2(Cp‴Co)(μ3,η2:η2:η2-As3)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.