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Exploring Coordination Modes: Late Transition Metal Complexes with a Methylene‐bridged Macrocyclic Tetra‐NHC Ligand
Author(s) -
Altmann Philipp J.,
Weiss Daniel T.,
Jandl Christian,
Kühn Fritz E.
Publication year - 2016
Publication title -
chemistry – an asian journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.18
H-Index - 106
eISSN - 1861-471X
pISSN - 1861-4728
DOI - 10.1002/asia.201600198
Subject(s) - ligand (biochemistry) , transmetalation , chemistry , methylene , transition metal , palladium , coordination complex , metal , nickel , coordination geometry , macrocyclic ligand , crystallography , carbene , stereochemistry , photochemistry , molecule , medicinal chemistry , organic chemistry , catalysis , biochemistry , hydrogen bond , receptor
A tetranuclear silver(I) N ‐heterocyclic carbene (NHC) complex bearing a macrocyclic, exclusively methylene‐bridged, tetracarbene ligand was synthesized and employed as transmetalation agent for the synthesis of nickel(II), palladium(II), platinum(II), and gold(I) derivatives. The transition metal complexes exhibit different coordination geometries, the coinage metals being bound in a linear fashion forming molecular box‐type complexes, whereas the group 10 metals adapt an almost ideal square planar coordination geometry within the ligand's cavity, resulting in saddle‐shaped complexes. Both the Ag I and the Au I complexes show ligand‐induced metal–metal contacts, causing photoluminescence in the blue region for the gold complex. Distinct metal‐dependent differences of the coordination behavior between the group 10 transition metals were elucidated by low‐temperature NMR spectroscopy and DFT calculations.