Solid-State Isolation of Cyclic Alkyl(Amino) Carbene (cAAC)-Supported Structurally Diverse Alkali Metal-Phosphinidenides |
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| Authors: | Aditya Kulkarni Selvakumar Arumugam Maria Francis Pulikanti Guruprasad Reddy Ekta Nag Sai Manoj N. V. T. Gorantla Dr. Kartik Chandra Mondal Dr. Sudipta Roy |
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| Affiliation: | 1. Department of Chemistry, Indian Institute of Science Education and Research (IISER), Tirupati, 517507 India;2. Department of Chemistry, Indian Institute of Technology Madras, Chennai, 600036 India |
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| Abstract: | Cyclic alkyl(amino) carbene (cAAC)-supported, structurally diverse alkali metal-phosphinidenides 2 – 5 of general formula ((cAAC)P-M)n(THF)x [ 2 : M=K, n=2, x=4; 3 : M=K, n=6, x=2; 4 : M=K, n=4, x=4; 5 : M=Na, n=3, x=1] have been synthesized by the reduction of cAAC-stabilized chloro-phosphinidene cAAC=P-Cl ( 1 ) utilizing metallic K or KC8 and Na-naphthalenide as reducing agents. Complexes 2 – 5 have been structurally characterized in solid state by NMR studies and single crystal X-ray diffraction. The proposed mechanism for the electron transfer process has been well-supported by cyclic voltammetry (CV) studies and Density Functional Theory (DFT) calculations. The solid state oligomerization process has been observed to be largely dependent on the ionic radii of alkali metal ions, steric bulk of cAAC ligands and solvation/de-solvation/recombination of the dimeric unit [(cAAC)P-M(THF)x]2. |
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| Keywords: | cyclic alkyl(amino) carbene cyclic voltammetry DFT calculations oligomerization phosphinidenide |
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