TY - JOUR
T1 - Exploring Coordination Modes
T2 - Late Transition Metal Complexes with a Methylene-bridged Macrocyclic Tetra-NHC Ligand
AU - Altmann, Philipp J.
AU - Weiss, Daniel T.
AU - Jandl, Christian
AU - Kühn, Fritz E.
N1 - Publisher Copyright:
© 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
PY - 2016/5/20
Y1 - 2016/5/20
N2 - 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 AgI and the AuI 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. Ag complex issue: A tetranuclear silver complex bearing an exclusively methylene-bridged, macrocyclic NHC ligand is synthesized and employed as transmetalation reagent for the synthesis of a series of d-block metal complexes. Their structural characteristics, photoluminescent properties, and ligand dynamics were investigated by X-ray crystallography, NMR spectroscopy, absorption and emission spectroscopy as well as DFT calculations.
AB - 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 AgI and the AuI 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. Ag complex issue: A tetranuclear silver complex bearing an exclusively methylene-bridged, macrocyclic NHC ligand is synthesized and employed as transmetalation reagent for the synthesis of a series of d-block metal complexes. Their structural characteristics, photoluminescent properties, and ligand dynamics were investigated by X-ray crystallography, NMR spectroscopy, absorption and emission spectroscopy as well as DFT calculations.
KW - late transition metals
KW - macrocyclic ligands
KW - N-heterocyclic carbenes
KW - photoluminescence
KW - transmetalation
UR - http://www.scopus.com/inward/record.url?scp=84969157733&partnerID=8YFLogxK
U2 - 10.1002/asia.201600198
DO - 10.1002/asia.201600198
M3 - Article
AN - SCOPUS:84969157733
SN - 1861-4728
VL - 11
SP - 1597
EP - 1605
JO - Chemistry - An Asian Journal
JF - Chemistry - An Asian Journal
IS - 10
ER -