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N‐Heterocyclic Carbene Stabilized Dicarbondiphosphides: Strong Neutral Four‐Membered Heterocyclic 6π‐Electron Donors
Author(s) -
Li Zhongshu,
Chen Xiaodan,
Liu Liu Leo,
Scharnhölz Moritz Theodor,
Grützmacher Hansjörg
Publication year - 2020
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201914015
Subject(s) - carbene , chemistry , ring (chemistry) , conjugated system , crystallography , aromaticity , spectroscopy , stereochemistry , infrared spectroscopy , medicinal chemistry , molecule , catalysis , organic chemistry , polymer , physics , quantum mechanics
In contrast to cyclic π‐conjugated hydrocarbons, the coordination chemistry of inorganic heterocycles is less developed. Dicarbondiphosphides stabilized by N‐heterocyclic carbenes (NHCs) NHC→C 2 P 2 ←NHC ( 1 a , b ) (NHC=IPr or SIPr) contain a four‐membered C 2 P 2 ring with an aromatic 6π‐electron configuration. These heterocycles coordinate to a variety of complex fragments with metals from groups 6, 9, and 10, namely [M 0 (CO) 3 ] (M=Cr, Mo), [Co I (CO) 2 ] + , or [Ni II Br 2 ], through an η 4 ‐coordination mode, leading to complexes 2 a , b , 3 a , b , 5 a , b , and 6 a , b , respectively. These complexes were characterized by X‐ray diffraction methods using single crystals, IR spectroscopy, and DFT calculations. In combination these methods indicate that 1 a , b behave as exceptionally strong 6π‐electron donors.