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Solid‐State Isolation of Cyclic Alkyl(Amino) Carbene (cAAC)‐Supported Structurally Diverse Alkali Metal‐Phosphinidenides
Author(s) -
Kulkarni Aditya,
Arumugam Selvakumar,
Francis Maria,
Reddy Pulikanti Guruprasad,
Nag Ekta,
Gorantla Sai Manoj N. V. T.,
Mondal Kartik Chandra,
Roy Sudipta
Publication year - 2021
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.202003505
Subject(s) - carbene , steric effects , chemistry , crystallography , ionic radius , alkali metal , solvation , ionic bonding , cyclic voltammetry , density functional theory , alkyl , metal , stereochemistry , ion , computational chemistry , organic chemistry , electrochemistry , electrode , catalysis
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 KC 8 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 .