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μ‐Imido, μ‐(η 2 ,η 2 ‐N,N‐Hydrazido) and μ‐(η 1 ‐C:η 2 ‐C,N‐Isocyanido) Dinuclear (Fulvalene)zirconium Derivatives
Author(s) -
GonzálezMaupoey Marta,
Rodríguez Gema M.,
Cuenca Tomás
Publication year - 2002
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/1099-0682(200208)2002:8<2057::aid-ejic2057>3.0.co;2-p
Subject(s) - chemistry , zirconium , medicinal chemistry , toluene , anhydrous , inorganic chemistry , organic chemistry
Treatment of the chloro(fulvalene)zirconium(III) compound [Zr(η 5 ‐C 5 H 5 )(μ‐Cl)] 2 [μ‐(η 5 ,η 5 ‐C 10 H 8 )] with an equimolar amount of azobenzene in toluene, under extremely anhydrous conditions, gives the μ‐[bis(imido)] derivative [Zr(η 5 ‐C 5 H 5 )(μ‐NPh)] 2 [μ‐(η 5 ,η 5 ‐C 10 H 8 )] ( 1 ). However, when this reaction is carried out under insufficiently dry conditions a mixture of the previously reported μ‐oxo complex [Zr(η 5 ‐C 5 H 5 )Cl] 2 (μ‐O)[μ‐(η 5 ,η 5 ‐C 10 H 8 )] and 1,2‐diphenylhydrazine is obtained. When the chloro(fulvalene)zirconium(III) compound reacts with benzo[ c ]cinnoline the μ‐(η 2 ,η 2 ‐N,N‐hydrazido) complex [Zr(η 5 ‐C 5 H 5 )Cl] 2 [μ‐(NC 6 H 4 C 6 H 4 N)][μ‐(η 5 ,η 5 ‐C 10 H 8 )] ( 2a ) is obtained, which rearranges to the thermodynamically more stable 2b . Addition of an equimolar amount of RNC (R = n Bu, C 6 H 11 ) to a toluene solution of [Zr(η 5 ‐C 5 H 5 )(μ‐Cl)] 2 [μ‐(η 5 ,η 5 ‐C 10 H 8 )] gives [Zr(η 5 ‐C 5 H 5 )Cl] 2 (μ‐CNR)[μ‐(η 5 ,η 5 ‐C 10 H 8 )] [R = n Bu ( 3 ), C 6 H 11 ( 4 )]. Reaction of [Zr(η 5 ‐C 5 H 5 )Cl] 2 (μ‐CN t Bu)[μ‐(η 5 ,η 5 ‐C 10 H 8 )] with 1 equiv. of PhCH 2 MgCl or (PhCH 2 ) 2 Mg(THF) 2 afforded the monobenzyl derivatives [Zr(η 5 ‐C 5 H 5 )] 2 (CH 2 Ph)(Cl)(μ‐CN t Bu)[μ‐(η 5 ,η 5 ‐C 10 H 8 )] ( 5 and 6 ). When this reaction was carried out with 2 equiv. or an excess of PhCH 2 MgCl, a mixture of the monobenzyl and dibenzyl compounds [Zr(η 5 ‐C 5 H 5 )] 2 (CH 2 Ph)(Cl)(μ‐CN t Bu)[μ‐(η 5 ,η 5 ‐C 10 H 8 )] ( 5 ) and [Zr(η 5 ‐C 5 H 5 )(CH 2 Ph)] 2 (μ‐CN t Bu)[μ‐(η 5 ,η 5 ‐C 10 H 8 )] ( 7 ) is obtained. Similar reactions with 1 or 2 equiv. of (CH 3 ) 3 SiCH 2 Li afford a mixture of the monoalkyl and dialkyl compounds [Zr(η 5 ‐C 5 H 5 )] 2 [CH 2 Si(CH 3 ) 3 ](Cl)(μ‐CN t Bu)[μ‐(η 5 ,η 5 ‐C 10 H 8 )] ( 8 ) and {Zr(η 5 ‐C 5 H 5 )[CH 2 Si(CH 3 ) 3 ]} 2 (μ‐CN t Bu)[μ‐(η 5 ,η 5 ‐C 10 H 8 )] ( 9 ) compounds. Moreover, methylation of [Zr(η 5 ‐C 5 H 5 )Cl] 2 (μ‐CN n Bu)[μ‐(η 5 ,η 5 ‐C 10 H 8 )] gives the analytically pure tetramethyl derivative [Zr(η 5 ‐C 5 H 5 )(CH 3 )] 2 (μ‐CN n Bu)[μ‐(η 5 ,η 5 ‐C 10 H 8 )] ( 10 ), whereas [Zr(η 5 ‐C 5 H 5 )Cl] 2 (μ‐CNC 6 H 11 )[μ‐(η 5 ,η 5 ‐C 10 H 8 )] reacts with MeLi to give a mixture of the monomethyl derivatives [Zr(η 5 ‐C 5 H 5 )] 2 (CH 3 )(Cl)(μ‐CNC 6 H 11 )[μ‐(η 5 ,η 5 ‐C 10 H 8 )] ( 11 and 12 ), as well as the dimethyl compound [Zr(η 5 ‐C 5 H 5 )(CH 3 )] 2 (μ‐CNC 6 H 11 )[μ‐(η 5 ,η 5 ‐C 10 H 8 )] ( 13 ). (© Wiley‐VCH Verlag GmbH, 69451 Weinheim, Germany, 2002)