Dinuclear zirconium complexes with Me2Si(C5H4)2as bridging ligand. Molecular structure of [{Zr(η5-C5H3-But2)Me}2(µ-O){µ-Me2Si(C5H4)2}]
- 1 January 1995
- journal article
- Published by Royal Society of Chemistry (RSC) in J. Chem. Soc., Dalton Trans.
- No. 2,p. 231-236
- https://doi.org/10.1039/dt9950000231
Abstract
The reaction of Li2[Me2Si(C5H4)2] with 2 equivalents of [ZrLCl3](L = C5Me5 or C5H3But 2) in toluene under reflux gave the known [{Zr(C5Me5)Cl2}2{µ-Me2Si(C5H4)2}]1 and the new chloro derivative [{Zr(C5H3But 2)Cl2}2{µ-Me2Si(C5H4)2}]2 in good yields. Addition of 4 equivalents of LiMe (or MgMeCl) to a pentane solution of 1 or 2 afforded the tetramethyl derivatives [{Zr(C5Me5)Me2}2{µ-Me2Si(C5H4)2}]3 and [{Zr(C5H3But 2)Me2}2{µ-Me2Si(C5H4)2}]4. Compound 3 is extremely moisture sensitive leading to the µ-oxo dinuclear complex [{Zr(C5Me5)Me}2(µ-O){µ-Me2Si(C5H4)2}]5, as demonstrated by 1H NMR spectroscopy. Compound 4 reacted with water, in pentane or toluene, to give the µ-oxo dimethyl complex [{Zr(C5H3But 2)Me}2(µ-O){µ-Me2Si(C5H4)2}]6. Further reaction of 6 with water in toluene gave an unidentified insoluble yellow powder through the intermediate formation of a µ-dioxo methyl complex 7, identified by 1H NMR spectroscopy. The crystal structure of 6 has been determined by X-ray diffraction methods: monoclinic, space group P21/n, a= 15.494(4), b= 13.338(3), c= 19.933(4)Å, β= 107.19(1)° and Z= 4. Complex 6 is a dimer produced by the interaction of two Zr(η5-C5H3But 2) Me units bridged by one oxygen atom and the Me2Si(C5H4)2 group.Keywords
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