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Preparation, Structures, and Properties of Dinuclear Ni and Pd Complexes of Tridentate Amine‐Chalcogenolate Ligands
Author(s) -
Kersting Berthold
Publication year - 1998
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/(sici)1099-0682(199808)1998:8<1071::aid-ejic1071>3.0.co;2-4
Subject(s) - chemistry , isostructural , amine gas treating , palladium , crystal structure , metal , crystallography , medicinal chemistry , stereochemistry , catalysis , organic chemistry
Abstract The preparation and characterization of dinuclear Ni II and Pd II complexes of the tridentate amine‐chalcogenolate ligands 4‐ tert ‐butyl‐2,6‐di(aminomethyl)thiophenol ( 4a ) and 4‐ tert ‐butyl‐2,6‐di(aminomethyl)selenophenol ( 4b ) are re‐ported. Reaction of 4a , b with Ni(ClO 4 ) 2 ·6 H 2 O or (COD)PdCl 2 in a 1:1 molar ratio yields 1:1 complexes of composition [M 2 (L) 2 ][BPh 4 ] 2 ·CH 3 CN·CH 3 OH [M = Ni, L = 4a , b ( 5a , b ); M = Pd, L = 4a,b ( 6a , b )]. The palladium complex 6a is isomorphous with 5a as shown by X‐ray crystal structure analysis. NMR studies reveal that both complexes retain their solid‐state structure in solution and that the selenolate complexes are isostructural with the thiolate complexes. All complexes undergo electrochemically reversible one‐electron transfer processes in the potential range –1.0 to –0.8 V vs. SCE ascribed to metal‐centered reductions with formation of mixed‐valent M I,II species [M 2 (L) 2 ] + . Further reduction at more negative potentials then leads to the neutral [M 2 (L) 2 ] species, which are not stable on the time scale of the CV experiment. The spectroscopic properties of the thiolate and selenolate complexes are very similar indicating electronically similar properties of the tridentate amine‐chalcogenolate ligands.