期刊
POLYHEDRON
卷 225, 期 -, 页码 -出版社
PERGAMON-ELSEVIER SCIENCE LTD
DOI: 10.1016/j.poly.2022.116055
关键词
Zinc; Cadmium; Imidazol-2-ylidene-N '-phenylthiourea; Guanidine; Metal sulfur complex
资金
- Science and Engineering Research Board (SERB)
- Department of Science and Technology (DST),Government of India [TAR/2020/000003]
- CSIR, India [09/1001 (0040) /2018- EMR-1]
We report the synthetic and structural studies of a series of zinc and cadmium metal complexes. The solid-state structures of these complexes were determined by single-crystal X-ray diffraction analysis. The zinc and cadmium complexes exhibited variations in coordination features and structures. Among them, the zinc complexes showed excellent catalytic activity.
We report the synthetic and structural studies of a series of zinc metal complexes, [(Im (R) NCSN(H)Ph)(2)ZnX2] (R = Mesityl (Mes), X = Cl (1a), Br (1b), I (1c); R = 2,6-Diisopropylphenyl (Dipp), X = Cl (2a), Br (2b), I (2c)) and the cadmium metal complexes [(Im (R) NCSN(H)Ph)(2)CdX2] (R = Mes, X = Cl (3a), I (3b)] and [(Im (R) NCSN(H)Ph)CdX](2) [R = Dipp, X = Cl (4a), I (4b)). The solid-state structures of metal complexes 1c, 2c, 3a, 4a, and 4b were established by single-crystal X-ray diffraction analysis. The zinc complexes 1c, 2c, and cadmium complex 3a are isostructural in solid-state, and in each case, the metal ion is ligated with two ligand moieties in a monodentate fashion via the sulfur atom. Despite similar coordination features, they exhibited a marked variation in the orientation of phenylthiourea scaffold as well as hydrogen-bonding interactions. The solid-state structures of cadmium complexes 4a and 4b involve a centrosymmetric dimer containing four-membered ring -[Cd-X-]2, formed by mu(2)-coordination of the halide group on each cadmium atom. In all the complexes, the metal ion (Zn2+/Cd2+) adopts a distorted tetrahedral MS2X2 environment. Additionally, the catalytic activity of [(Im(Mes)NCSN(H) Ph)(2)ZnI2] (1c) as an active pre-catalyst is reported in the N-H addition of amines to readily available carbo-diimides to produce a series of substituted guanidine derivatives in an excellent yield. The zinc complex 1c showed very good conversion and tolerance of a broad and valuable substrate scope during the guanidine formation.
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