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N‐Heterocyclic Carbene Complexes of Copper(I) Thiocyanate: Synthesis and Structural Characterization
Author(s) -
Dodds Christopher A.,
Kennedy Alan R.
Publication year - 2014
Publication title -
zeitschrift für anorganische und allgemeine chemie
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.354
H-Index - 66
eISSN - 1521-3749
pISSN - 0044-2313
DOI - 10.1002/zaac.201400036
Subject(s) - thiocyanate , chemistry , carbene , imes , monomer , crystallography , copper , crystal structure , intermolecular force , hydrogen bond , medicinal chemistry , stereochemistry , molecule , inorganic chemistry , organic chemistry , catalysis , polymer
The synthesis and characterization of three N‐heterocyclic carbene (NHC) complexes of copper(I) thiocyanate [Cu(IMes)(NCS)] 2 ( 1 ), [Cu(IXy)(NCS)] 2 ( 2 ), and [Cu(IPr)(NCS)] ( 3 ) [IMes = 1,3‐bis(2,4,6‐trimethylphenyl)imidazol‐2‐ylidene, IXy = 1,3‐bis(2,6‐dimethylphenyl)imidazol‐2‐ylidene, IPr = 1,3‐bis(2,6‐diisopropylphenyl)imidazol‐2‐ylidene] are described. Single crystal diffraction and IR spectroscopy shows that reaction of one equivalent of sodium thiocyanate with [Cu(NHC)Cl] results in the formation of solid‐state centrosymmetric dimers for 1 and 2 with bridging thiocyanate ligands bound through both N and S. In contrast, the equivalent reaction with IPr gives a monomeric species with N bound thiocyanate. In the solution state, all the structures of complexes 1 – 3 would appear to be monomeric, as evidenced by both solution state FT‐IR and 13 C NMR spectroscopic studies. In addition the precursor to complex 2 [Cu(IXy)Cl] ( 4 ) was structurally characterized by X‐ray diffraction revealing a one‐dimensional chain structure that propagates through C–H ··· Cl intermolecular interactions with both methyl and aromatic hydrogen atoms.