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A Neutral Tetraphosphacyclobutadiene Ligand in Cobalt(I) Complexes
Author(s) -
Yao Shenglai,
Lindenmaier Nils,
Xiong Yun,
Inoue Shigeyoshi,
Szilvási Tibor,
Adelhardt Mario,
Sutter Jörg,
Meyer Karsten,
Driess Matthias
Publication year - 2015
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201409469
Subject(s) - chemistry , cobalt , ligand (biochemistry) , electron paramagnetic resonance , reactivity (psychology) , cyclic voltammetry , crystallography , toluene , stereochemistry , medicinal chemistry , inorganic chemistry , electrochemistry , nuclear magnetic resonance , organic chemistry , medicine , biochemistry , physics , receptor , alternative medicine , electrode , pathology
The unusual reactivity of the newly synthesized β‐diketiminato cobalt(I) complexes, [(L Dep Co) 2 ] ( 2 a , L Dep =CH[C(Me)N(2,6‐Et 2 C 6 H 3 )] 2 ) and [L Dipp Co ⋅ toluene] ( 2 b , L Dipp =CH[CHN(2,6‐ i Pr 2 C 6 H 3 )] 2 ), toward white phosphorus was investigated, affording the first cobalt(I) complexes [(L Dep Co) 2 (μ 2 :η 4 ,η 4 ‐P 4 )] ( 3 a ) and [(L Dipp Co) 2 (μ 2 :η 4 ,η 4 ‐P 4 )] ( 3 b ) bearing the neutral cyclo‐P 4 ligand with a rectangular‐planar structure. The redox chemistry of 3 a and 3 b was studied by cyclic voltammetry and their chemical reduction with one molar equivalent of potassium graphite led to the isolation of [(L Dep Co) 2 (μ 2 :η 4 ,η 4 ‐P 4 )][K(dme) 4 ] ( 4 a ) and [(L Dipp Co) 2 (μ 2 :η 4 ,η 4 ‐P 4 )][K(dme) 4 ] ( 4 b ). Unexpectedly, the monoanionic Co 2 P 4 core in 4 a and 4 b , respectively, contains the two‐electron‐reduced cyclo‐P 4 2− ligand with a square‐planar structure and mixed‐valent cobalt(I,II) sites. The electronic structures of 3 a , 3 b , 4 a , and 4 b were elucidated by NMR and EPR spectroscopy as well as magnetic measurements and are in agreement with results of broken‐symmetry DFT calculations.