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Calcium Complexes Having Different Amidinate Ligands ‐ Synthesis and Structural Diversity
Author(s) -
Anga Srinivas,
Bhattacharjee Jayeeta,
Banerjee Indrani,
Nayek Hari Pada,
Panda Tarun K.
Publication year - 2016
Publication title -
chemistryselect
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.437
H-Index - 34
ISSN - 2365-6549
DOI - 10.1002/slct.201600299
Subject(s) - chemistry , homoleptic , diimine , ligand (biochemistry) , anhydrous , medicinal chemistry , stereochemistry , alkyl , yield (engineering) , coordination sphere , crystal structure , organic chemistry , metal , catalysis , biochemistry , materials science , receptor , metallurgy
A one‐pot reaction of α‐diimine ligand 1,4‐disubstituted diazabutadienes (DAD) with potassium benzyl and anhydrous calcium iodide in 1:1:1 molar ratio afforded unprecedented 3‐phenylprop‐2‐ene‐di‐amido calcium compound [ κ 2 ‐(THF) 4 Ca{DippNC(=CHPh)CH 2 NDipp}] ( 1 ) (Dipp = 2,6‐diisopropylphenyl) in good yield. The solid‐state structure of the compound 1 revealed the formation of dianionic 3‐phenylprop‐2‐ene‐di‐amido ligand having an exocyclic olefinic bond derived from neutral α‐diimine fragment. However, analogous reactions with three different carbodiimides (RN=C=NR; R=Cy, iPr and t Bu) with alkyl potassium and anhydrous calcium diiodide yielded corresponding homoleptic calcium compounds with amidinato ligand [ κ 2 ‐(THF) 2 Ca{RN=C(CH 2 Ph)NR} 2 ] [R=Cy ( 2 ), i Pr ( 3 ) and t Bu ( 4 )]. A separate reaction of DAD ligand, LiCH 2 SiMe 3 and anhydrous ZnCl 2 in diethylether solvent produced tri‐coordinated zinc compound [ κ 2 ‐ {DippN=C(CH 2 SiMe 3 )CH 2 NDipp}Zn[ κ 1 ‐{DippN=C(CH 2 SiMe 3 )CH 2 N‐Dipp}] ( 5 ) having amidinato moieties in the zinc coordination sphere in high yield. Molecular structures of compounds 2–5 in their solid states were also established.