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Structural characterization of the derivatives of bis{[2,6‐(dimethylamino)methyl]phenyl} selenide with palladium(II) and mercury(II)
Author(s) -
Gupta Anand,
Deka Rajesh,
Butcher Ray J.,
Singh Harkesh B.
Publication year - 2020
Publication title -
acta crystallographica section c
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.304
H-Index - 17
ISSN - 2053-2296
DOI - 10.1107/s2053229620010311
Subject(s) - homoleptic , chemistry , selenide , moiety , molecule , palladium , medicinal chemistry , stereochemistry , ligand (biochemistry) , halide , crystal structure , chloride , crystallography , catalysis , selenium , metal , inorganic chemistry , organic chemistry , biochemistry , receptor
The intramolecularly coordinated homoleptic diorgano selenide bis{2,6‐bis[(dimethylamino)methyl]phenyl} selenide, C 24 H 38 N 4 Se or R 2 Se, where R is 2,6‐(Me 2 NCH 2 ) 2 C 6 H 3 , 14 , was synthesized and its ligation reactions with Pd II and Hg II precursors were explored. The reaction of 14 with SO 2 Cl 2 and K 2 PdCl 4 resulted in the formation of the meta C—H‐activated dipalladated complex {μ‐2,2′‐bis[(dimethylamino)methyl]‐4,4′‐bis[(dimethylazaniumyl)methyl]‐3,3′‐selanediyldiphenyl‐κ 4 C 1 , N 2 : C 1′ , N 2′ }bis[dichloridopalladium(II)], [Pd 2 Cl 4 (C 24 H 38 N 4 Se)] or [{ R (H)PdCl 2 } 2 Se], 15 . On the other hand, when ligand 14 was reacted with HgCl 2 , the reaction afforded a dimercurated selenolate complex, {μ‐bis{2,6‐bis[(dimethylamino)methyl]benzeneselanolato‐κ 4 N 2 , Se : Se , N 6 }‐μ‐chlorido‐bis[chloridomercury(II)], [Hg 2 (C 12 H 19 N 2 Se)Cl 3 ] or R SeHg 2 Cl 3 , 16 , where two Hg II ions are bridged by selenolate and chloride ligands. In palladium complex 15 , there are two molecules located on crystallographic twofold axes and within each molecule the Pd moieties are related by symmetry, but there are still two independent Pd centers. Mercury complex 16 results from the cleavage of one of the Se—C bonds to form a bifurcated SeHg 2 moiety with the formal charge on the Se atom being −1. In addition, one of the Cl ligands bridges the two Hg atoms and there are two terminal Hg—Cl bonds. Each Hg atom is in a distorted environment which can be best described as a T‐shaped base with the bridging Cl atom in an apical position, with several angles close to 90° and with one angle much larger and closer to 180°.