Mononuclear five- and six-coordinate iron hydrazido and hydrazine species.
Mononuclear five- and six-coordinate iron hydrazido and hydrazine species.
复制标题
单核五配位和六配位铁酰肼和肼物种。
DOI：
10.1021/ic301704f
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发表时间：
2012
影响因子：
4.6
通讯作者：
Peters,JonasC
中科院分区：
文献类型：
--
作者：
Saouma,CarolineT;Lu,ConnieC;Peters,JonasC
本文介绍了几个低自旋铁（II）配合物，协调肼（N2 H4），肼基（N2 H3-），和氨的合成和表征。引入空间位阻的三（二间三苯膦基）硼酸盐配体[PhBPmter 3]−，以提供无法用[PhBPPh 3]−配体稳定的物质（[PhBPR 3]−= PhB（CH 2 PR 2）3-）。用肼处理[PhBPmter 3]FeMe产生不寻常的5-配位酰肼配合物[PhBPmter 3]Fe（η2-N2 H3）（1），其中酰肼作为L2 X型配体。在配位L型配体时，酰肼基转变为LX型配体，生成[PhBPmter 3]Fe（L）（η2-N2 H3）（L = N2 H4（2）或NH3（3））。相反，用肼处理[PhBPPh 3]FeMe形成加合物[PhBPPh 3]Fe（Me）（η2-N2 H4）（5）。配合物5对甲烷热不稳定，生成中间体[PhBPPh 3]Fe（η2-N2 H3），其经双分子偶联生成{[PhBPPh 3]Fe}2（μ-η1：η1-N2 H4）（μ-η2：η2-N2 H2）。这些和相关的肼和酰肼物种的氧化。例如，1或5与Pb（OAc）4的氧化导致N2 Hx配体（x= 3，4）的反离子化，并形成[PhBPR 3]Fe（NH3）（OAc）（R = Ph（9）andmter（11））。
This article describes the synthesis and characterization of several low-spin iron(II) complexes that coordinate hydrazine (N2H4), hydrazido (N2H3–), and ammonia. The sterically encumbered tris(di-meta-terphenylphosphino)borate ligand, [PhBPmter3]−, is introduced to provide access to species that cannot be stabilized with the [PhBPPh3]−ligand ([PhBPR3]−= PhB(CH2PR2)3–). Treatment of [PhBPmter3]FeMe with hydrazine generates the unusual 5-coordinate hydrazido complex [PhBPmter3]Fe(η2-N2H3) (1), in which the hydrazido serves as an L2X-type ligand. Upon coordination of an L-type ligand, the hydrazido shifts to an LX-type ligand, generating [PhBPmter3]Fe(L)(η2-N2H3) (L = N2H4(2) or NH3(3)). In contrast, treatment of [PhBPPh3]FeMe with hydrazine forms the adduct [PhBPPh3]Fe(Me)(η2-N2H4) (5). Complex5is thermally unstable to methane loss, generating intermediate [PhBPPh3]Fe(η2-N2H3), which undergoes bimolecular coupling to produce {[PhBPPh3]Fe}2(μ-η1:η1-N2H4)(μ-η2:η2-N2H2). The oxidation of these and related hydrazine and hydrazido species is also presented. For example, oxidation of1or5with Pb(OAc)4results in disproportionation of the N2Hxligand (x= 3, 4), and formation of [PhBPR3]Fe(NH3)(OAc) (R = Ph (9) andmter (11)).