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Syntheses and Characterization of Half‐Sandwich Zirconium Complexes with Dichalcogenolate o ‐Carborane Ligands
Author(s) -
XiaoYan Yu,
GuoXin Jin,
NingHai Hu
Publication year - 2003
Publication title -
chinese journal of chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.28
H-Index - 41
eISSN - 1614-7065
pISSN - 1001-604X
DOI - 10.1002/cjoc.20030210419
Subject(s) - chemistry , dilithium , zirconium , ligand (biochemistry) , cyclopentadienyl complex , metallocene , sulfur , ring (chemistry) , yield (engineering) , crystallography , carborane , coordination sphere , medicinal chemistry , stereochemistry , ion , inorganic chemistry , crystal structure , organic chemistry , deprotonation , catalysis , metallurgy , biochemistry , polymer , receptor , materials science , polymerization
Metallocene complex Cp 2 # ZrCl 2 (Cp # = η 5– 1,3‐ t Bu 2 C 5 H 3 ) (1) has been prepared from the reaction of LiCp # with ZrCl 4 in good yield. Reactions of 1 with dilithium dichalcogenolate o ‐carboranes afforded new type of half‐sandwich compounds with dichalcogenolate o ‐carboranyl ligands, [Li(THF) 4 ][Cp # Zr(E 2 C 2 B 10 H 10 ) 2 ] (E=S, 2a; E= Se, 2b) in which only one cyclopentadienyl ring ligand existed. Complexes 1 and 2a were structurally characterized by X‐ray analyses. In complex 2a, the Zr(IV) ion is η 5 ‐bound to one 1,3‐di‐ tert ‐cydopentadienyl ring and s̀‐bound to four μ 2 ‐sulfur atoms of two dithio‐carboranes. The zirconium atom and four sulfur atoms form a distorted pyramid. The coordination sphere around the zirconium atom resembles in a piano stool structure with four legs of sulfur atoms and the fulcrum at the zirconium atom.