The Cobalt cyclo-P₄ Sandwich Complex and Its Role in the Formation of Polyphosphorus Compounds

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• 作者：Dr. Fabian Dielmann ; Prof. Dr. Alexey Timoshkin ; M. Sc. Martin Piesch ; Dr. Gá ; bor Balá ; zs and Prof. Dr. Manfred Scheer
• 刊名：Angewandte Chemie International Edition
• 出版年：2017
• 出版时间：February 1, 2017
• 年：2017
• 卷：56
• 期：6
• 页码：1671-1675
• 全文大小：2090K
• ISSN：1521-3773

文摘

A synthetic approach to the sandwich complex [Cp′′′Co(η⁴-P₄)] (2) containing a cyclo-P₄ ligand as an end-deck was developed. Complex 2 is the missing homologue in the series of first-row cyclo-P_n sandwich complexes, and shows a unique tendency to dimerize in solution to form two isomeric P₈ complexes [(Cp′′′Co)₂(μ,η⁴:η²:η¹-P₈)] (3 and 4). Reactivity studies indicate that 2 and 3 react with further [Cp′′′Co] fragments to give [(Cp′′′Co)₂(μ,η²:η²-P₂)₂] (5) and [(Cp′′′Co)₃P₈] (6), respectively. Furthermore, complexes 2, 3, and 4 thermally decompose forming 5, 6, and the P₁₂ complex [(Cp′′′Co)₃P₁₂] (7). DFT calculations on the P₄ activation process suggest a η³-P₄ Co complex as the key intermediate in the synthesis of 2 as well as in the formation of larger polyphosphorus complexes via a unique oligomerization pathway.