Organoiron compounds derived from the indium 'carbene analogues', [In(N(Ar)C(Me))2CH] (Ar = dipp = 2,6-iPr2C6H3; = Mes = 2,4,6-Me3C6H2).
Organoiron compounds derived from the indium 'carbene analogues', [In(N(Ar)C(Me))2CH] (Ar = dipp = 2,6-iPr2C6H3; = Mes = 2,4,6-Me3C6H2).
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DOI：
10.1039/b801160e
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发表时间：
2008-05
影响因子：
4
通讯作者：
M. Hill;P. Hitchcock;R. Pongtavornpinyo
中科院分区：
文献类型：
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作者：
M. Hill;P. Hitchcock;R. Pongtavornpinyo
[In(N(Dipp)C(Me))2CH](Ar=Dipp=2，6-iPr2C6H3；Ar=Mes=2，4，6-Me3C6H2)进入[CPFe(CO)2I]的Fe-I键，在温和的条件下生成In(III)化合物[CH(CH3)2CN-2，6-iPr2C6H3)2In(I)FeCp(CO)2]和[CH(CH3)2CN-2，4，6-Me3C6H3)2In(I)FeCp(CO)2]。试图从[CH(CH3)2CN-2，6-iPr2C6H3)2In(I)FeCp(CO)2]中提取碘阴离子以形成含有配位铟二基的阳离子物种的尝试失败了，并导致了从其中分离出两个离子物种的复杂的产物混合物。X-射线单晶分析表明，两种阳离子均不含铟。这些观察表明，正如以前的工作人员所注意到的那样，分解途径界定不明确。进一步尝试形成含有配位[In(N(Dipp)C(Me))2CH]片段的阳离子铁物种，导致铁中心从Fe(II)氧化到Fe(III)，并沉积了铟金属，并分离出阳离子Fe(III)-β-二酮基二亚胺配合物。
Oxidative insertion of the In(I) 'carbene analogues', [In{N(Dipp)C(Me))2CH] (Ar = Dipp = 2,6-iPr2C6H3; Ar = Mes = 2,4,6-Me3C6H2) into the Fe-I bond of [CpFe(CO)2I] occurred cleanly and under mild conditions to yield the In(III) compounds [CH((CH3)2CN-2,6-iPr2C6H3)2In(I)FeCp(CO)2] and [CH( (CH3)2CN-2,4,6-Me3C6H3)2In(I)FeCp(CO)2], which have been fully characterised in solution and the solid state. Attempts to abstract the iodide anion from [CH( (CH3)2CN-2,6-iPr2C6H3)2In(I)FeCp(CO)2] to form cationic species containing a coordinated indium diyl were unsuccessful and resulted in a complex mixture of products from which two ionic species were isolated. Neither cation was found to contain indium by X-ray crystallographic analysis. These observations were indicative of ill-defined decomposition pathways as have been noted by previous workers. A further attempt to form a cationic iron species containing a coordinated [In(N(Dipp)C(Me) )2CH] fragment resulted in oxidation of the iron centre from Fe(II) to Fe(III), with deposition of indium metal, and the isolation of a cationic Fe(III) beta-diketiminate complex.