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Isolable Ethylene Complexes of Copper(I), Silver(I), and Gold(I) Supported by Fluorinated Scorpionates [HB{3‐(CF3),5‐(CH3)Pz}3]– and [HB{3‐(CF3),5‐(Ph)Pz}3]–
Author(s) -
Ridlen Shawn G.,
Wu Jiang,
Kulkarni Naveen V.,
Dias H. V. Rasika
Publication year - 2016
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.201501365
Subject(s) - chemistry , ethylene , adduct , metal , copper , nuclear magnetic resonance spectroscopy , crystallography , medicinal chemistry , metathesis , stereochemistry , catalysis , organic chemistry , polymerization , polymer
The group 11 metal adducts [HB{3‐(CF 3 ),5‐(CH 3 )Pz} 3 ]M(C 2 H 4 ) (M = Au, Ag, and Cu; Pz = pyrazolyl) have been synthesized via a metathesis process using [HB{3‐(CF 3 ),5‐(CH 3 )Pz} 3 ]Na and CF 3 SO 3 Cu, CF 3 SO 3 Ag, AuCl and ethylene. The related [HB{3‐(CF 3 ),5‐(Ph)Pz} 3 ]Ag(C 2 H 4 ) has also been synthesized using [HB{3‐(CF 3 ),5‐(Ph)Pz} 3 ]Na(THF), CF 3 SO 3 Ag and ethylene. These group 11 metal ethylene complexes are white solids and form colorless crystals. They have been characterized by NMR spectroscopy and X‐ray crystallography. The gold‐ethylene adduct [HB{3‐(CF 3 ),5‐(CH 3 )Pz} 3 ]Au(C 2 H 4 ) shows large upfield NMR shifts of the ethylene proton and carbon signals relative to the corresponding peaks of the free ethylene, indicating relatively high Au→ethylene backbonding. NMR chemical shift data suggest that the silver complexes of both the tris(pyrazolyl)borate ligands [HB{3‐(CF 3 ),5‐(CH 3 )Pz} 3 ] – and [HB{3‐(CF 3 ),5‐(Ph)Pz} 3 ] – exhibit the weakest interaction with ethylene as compared to the respective copper and gold complexes. X‐ray crystal structures reveal that the gold atom in [HB{3‐(CF 3 ),5‐(CH 3 )Pz} 3 ]Au(C 2 H 4 ) binds to scorpionate in κ 2 ‐fashion while the related silver adduct features a κ 3 ‐bonded scorpionate. [HB{3‐(CF 3 ),5‐(CH 3 )Pz} 3 ]Cu(C 2 H 4 ) has a scorpionate that binds to copper with two short Cu–N bonds and one long Cu–N distance.