A neutral tetraphosphacyclobutadiene ligand in cobalt(I) complexes

Shenglai Yao, Nils Lindenmaier, Yun Xiong, Shigeyoshi Inoue, Tibor Szilvási, Mario Adelhardt, Jörg Sutter, Karsten Meyer, Matthias Driess

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The unusual reactivity of the newly synthesized β-diketiminato cobalt(I) complexes, [(LDepCo)2] (2a, LDep = CH[C(Me)N(2,6-Et2C6H3)]2) and [LDippCo·toluene] (2b, LDipp = CH[CHN(2,6-iPr2C6H3)]2), toward white phosphorus was investigated, affording the first cobalt(I) complexes [(LDepCo)2244-P4)] (3a) and [(LDippCo)2244-P4)] (3b) bearing the neutral cyclo-P4 ligand with a rectangular-planar structure. The redox chemistry of 3a and 3b was studied by cyclic voltammetry and their chemical reduction with one molar equivalent of potassium graphite led to the isolation of [(LDepCo)2244-P4)][K(dme)4] (4a) and [(LDippCo)2244-P4)][K(dme)4] (4b). Unexpectedly, the monoanionic Co2P4 core in 4a and 4b, respectively, contains the two-electron-reduced cyclo-P42- ligand with a square-planar structure and mixed-valent cobalt(I,II) sites. The electronic structures of 3a, 3b, 4a, and 4b were elucidated by NMR and EPR spectroscopy as well as magnetic measurements and are in agreement with results of broken-symmetry DFT calculations.

Original languageEnglish
Pages (from-to)1250-1254
Number of pages5
JournalAngewandte Chemie International Edition in English
Issue number4
StatePublished - 19 Jan 2015
Externally publishedYes


  • Bond activation
  • Cobalt
  • Phosphorus
  • β-diketiminates


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