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Synthesis of Cobalt-Centered Inorganic Sandwich Complexes
Zi-Chuan Wang1,2, Xiao-Man Du2, Shuang Wang2
1Department of Chemistry, Fudan University, Shanghai 200433, China.
None:
Complete inorganic sandwich complexes with group 15 element rings at a single metal center have remained elusive for more than 30 years. Herein, we report that the readily accessible Zintl ion E73- (E = P, As) reacts with Co(II) sources to afford the first single-centered cobalt inorganic sandwiches, [(η3-E3)Co(η4-E4)]2-. This work also represents the first extension of inorganic sandwiching from phosphorus to arsenic analogues. Mechanistic studies on the Co-P system reveal a two-step pathway via a [Co(P7)2]4- intermediate that undergoes thermally induced P73- fragmentation and rearrangement. While Ti and Fe analogues can be accessed efficiently using the same P73- precursor, their transformation pathways differ, reflecting metal-dependent reactivity. The P73--based route also provides superior access to [Ti(η5-P5)2]2- under mild conditions, and [Fe(η4-P4)2]2- with higher yield and purity than the previous approach. These results suggest that P73- acts as a versatile phosphorus source for inorganic sandwich synthesis, wherein cobalt systems allow product distribution to be modulated by the solvent choice and reaction conditions.
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