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Preparation and Use of Carbonyl-decorated Carbenes in the Activation of White Phosphorus
Published on: October 3, 2014
O2 Activation at a Low-Valent P-Center: Isolation of a Cyclic Alkyl(Amino) Carbene (cAAC)-Phosphonate-Supported
Asutosh Patra1, Maria Francis1, Kishor Shinde1
1Department of Chemistry, Indian Institute of Science Education and Research (IISER), Tirupati 517619, Andhra Pradesh, India.
Abstract:
Herein, we explore the coordination behavior and O2-activation of molecular diphosphorus (P2) in the presence of CuX (X = Cl, Br), unraveling the phosphinidene nature of low-valent phosphorus atoms. Both mono- and dicuprated P2 complexes with general formula [(cAAC)2P2(CuX)n] (cAAC = cyclic alkyl(amino) carbene, n = 1, X = Cl (2a-2b), Br (2c); n = 2, X = Cl (3a-3b), Br (3c)) are isolated in the solid state. Aerial oxidation of bis-cAAC-supported P2 in the presence of Cu(I) ions afforded the paramagnetic dicationic Cu(II)6 cluster [Cu6II(Cy-cAAC-PO3)4O2Cl2][CuCl2]2 (4), stabilized by cAAC-phosphonate ligands with μ3-P atoms. EPR studies revealed the in situ generation of a P-centered monoradical intermediate upon exposure of the monocuprated P2 to atmospheric oxygen, followed by oxidation of Cu(I) to Cu(II). All complexes are structurally characterized by single-crystal X-ray diffraction. Quantum chemical calculations are performed to explore the nature of chemical bonding and the electron density distribution of 2 and 3. Mulliken spin density calculations revealed the open-shell nature of cluster 4, featuring the Cu(II) ions, which was further supported by XPS, EPR, and magnetic measurements.
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