摘要
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Treatment of the chloro(fulvalene)zirconium(III) compound [Zr(η~5-C_5H_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...
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Treatment of the chloro(fulvalene)zirconium(III) compound [Zr(η~5-C_5H_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_5H_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_5H_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_5H_5)Cl]_2[μ-(NC_6H_4C_6H_4N)][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 = nBu, C_6H_(11)) to a toluene solution of [Zr(η~5-C_5H_5)(μ-Cl)]_2[μ-(η~5,η~5-C_(10)H_8)] gives [Zr(η~5-C_5H_5)Cl]_2(μ-CNR)[μ-CNR)[μ-(η~5,η~5-C_(10)H_8)] [R = nBu (3), C_6H_(11) (4)]. Reaction of [Zr(η~5-C_5H_5)Cl]_2(μ-CNtBu)[μ-CNtBu)[μ-(η~5,η~5-C_(10)H_8)] with 1 equiv. of PhCH_2)_2Mg(THF)_2 afforded the monobenzyl derivatives [Zr(η~5-C_5H_5)]_2(CH_2Ph)(Cl)(μ-CNtBu)[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_2MgCl, a mixture of the monobenzyl and dibenzyl compounds [Zr(η~5-C_5H_5)]_2(CH_2Ph)(Cl)(μ-CNtBu)[μ-(η~5,η~5-C_(10)H_8)] (5) and [Zr(η~5-C_5H_5)(CH_2Ph)]_2(μ-CNtBu)[μ-CNtBu)[μ-(η~5,η~5-C_(10)H_8)] (7) is obtained. Similar reactions with 1 or 2 equiv. of (CH_3)_3SiCH_2Li afford a mixture of the monoalkyl and dialkyl compounds [Zr(η~5-C_5H_5)]_2[CH_2Si(CH_3)_3](Cl)(μ-CNtBu)[μ-(η~5,η~5-C_(10)H_8)] (8) and {Zr(η~5-C_5H_5)[CH_2Si(CH_3)_3]}_2(μ-CNtBu)[μ-(η~5,η~5-C_(10)H_8)] (9) compounds. Moreover, methylation of [Zr(η~5-C_5H_5)Cl]_2(μ-CNnBu)[μ-(η~5,η~5-C_(10)H_8)] gives the analytically pure tetramethyl derivative [Zr(η~5-C_5H_5)(CH_3)]_2(μ-CNnBu)[μ-(η~5,η~5-C_(10)H_8)] (10), whereas [Zr(η~5-C_5H_5)Cl]_2(μ-CNC_6H_(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_5H_5)]_2(CH_3)(Cl)(μ-CNC_6H_(11)[μ-(η~5,η~5-C_(10)H_8)] (11 and 12), as well as the dimethyl compound [Zr(η~5-C_5H_5)(CH_3)]_2(μ-CNC_6H_(11))[μ-(η~5,η~5-C_(10)H_8)] (13).
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