Iron and ruthenium complexes having a pincer-type ligand with two protic amidepyrazole arms: Structures and catalytic application
Iron and ruthenium complexes having a pincer-type ligand with two protic amidepyrazole arms: Structures and catalytic application
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DOI：
10.1016/j.poly.2017.08.044
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发表时间：
2017-09
期刊：
影响因子：
2.6
通讯作者：
Y. Nakahara;Tatsuro Toda;S. Kuwata
中科院分区：
文献类型：
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作者：
Y. Nakahara;Tatsuro Toda;S. Kuwata
本文报道了2，6-二（5-新戊酰胺基-1H-吡唑-3-基）吡啶（酰胺-LH_2）与铁、钌配位的配合物。FeCl 2·4 H2O与等摩尔的酰胺-LH 2反应，再加入两个三甲基膦和过量的三氟甲磺酸钠，得到钳形铁配合物[Fe（MeCN）（amide-LH 2）（PMe 3）2]（OTf）2（1b; OTf = OSO 2CF 3）。研究了氨基对肼类化合物与氨基反应的影响。配合物1b催化肼分解为氨和二氮，但催化活性低于But-LH 2类似物1a。对1 bas和钌配合物[{RuCl 2（PPh 3）2}2（μ2-amide-LH 2）2]（2 b）的X射线分析表明，侧链羧酰胺基团沿着吡唑NH单元在第二配位层中形成氢键。
This paper describes the iron and ruthenium complexes ligated by 2,6-di(5-pivalamido-1H-pyrazol-3-yl)pyridine (amide-LH2) bearing electron-withdrawing NHCOButgroups on the two protic pyrazole arms. Treatment of FeCl2·4H2O with an equimolar amount of amide-LH2followed by addition of two trimethylphosphine and an excess of sodium triflate gave the pincer-type iron complex [Fe(MeCN)(amide-LH2)(PMe3)2](OTf)2(1b; OTf = OSO2CF3). Impact of the amido groups in1bon the reactions with hydrazines was evaluated. Complex1bcatalyzed disproportionation of hydrazine into ammonia and dinitrogen, although the catalytic activity was lower than that of the But-LH2analogue1a. X-ray analysis of1bas well as the ruthenium complex [{RuCl2(PPh3)2}2(μ2-amide-LH2)2] (2b) revealed that the pendant carboxamide groups along with the pyrazole NH units are engaged in hydrogen bonds in the second coordination sphere.