锰和铁的五氯苯酚钳形配合物——空间位阻对结构和反应活性的影响
Manganese and iron PCP pincer complexes - the influence of sterics on structure and reactivity.
作者信息
Eder Wolfgang, Himmelbauer Daniel, Stöger Berthold, Veiros Luis F, Pignitter Marc, Kirchner Karl
机构信息
Institute of Applied Synthetic Chemistry, Vienna University of Technology, Getreidemarkt 9, A-1060 Vienna, Austria.
X-Ray Center, Vienna University of Technology, Getreidemarkt 9, A-1060 Vienna, Austria.
出版信息
Dalton Trans. 2021 Oct 12;50(39):13915-13924. doi: 10.1039/d1dt02407h.
The syntheses of various manganese and iron PCP pincer complexes a solvothermal oxidative addition methodology is described. Upon reacting [Mn(CO)] with the ligands (P(C-Br)P-iPr) (1a) and (P(C-Br)P-iPr) (1b), Mn(I) PCP pincer complexes [Mn(PCP-iPr)(CO)] (2a) and [Mn(-PCP-iPr)(CO)] (2b) were obtained. Protonation of 2a with HBF·EtO led to the formation of [Mn(κ,,-P(CH)P-iPr)(CO)]BF (3) featuring an η-C-H agostic bond. The solvothermal reaction of 1a with [Fe(CO)] afforded the Fe(II) PCP pincer complex [Fe(PCP-iPr)(CO)Br] (4). Treatment of 4 with Li[HBEt] afforded the Fe(I) complex [Fe(PCP-iPr)(CO)] (5a). When using the sterically more demanding ligands (P(C-Br)P-Bu) (1c) and (P(C-Br)P-Bu)(1d) striking differences in reactivity were observed. While neither 1c nor 1d showed any reactivity towards [Mn(CO)], the reaction with [Fe(CO)] and [Fe(CO)] led to the formation of the Fe(I) complexes [Fe(PCP-Bu)(CO)] (5b) and [Fe(PCP-Bu)(CO)] (5c). X-ray structures of representative complexes are provided.
描述了各种锰和铁的PCP钳形配合物的合成方法——溶剂热氧化加成法。使[Mn(CO)]与配体(P(C-Br)P-iPr)(1a)和(P(C-Br)P-iPr)(1b)反应，得到了锰(I)的PCP钳形配合物Mn(PCP-iPr)(CO)和Mn(-PCP-iPr)(CO)。用HBF·EtO对2a进行质子化反应，生成了具有η-C-H配位键的[Mn(κ,,-P(CH)P-iPr)(CO)]BF(3)。1a与[Fe(CO)]的溶剂热反应得到了铁(II)的PCP钳形配合物Fe(PCP-iPr)(CO)Br。用Li[HBEt]处理4得到了铁(I)配合物Fe(PCP-iPr)(CO)。当使用空间位阻更大的配体(P(C-Br)P-Bu)(1c)和(P(C-Br)P-Bu)(1d)时，观察到反应活性有显著差异。虽然1c和1d对[Mn(CO)]均无反应活性，但它们与[Fe(CO)]和[Fe(CO)]反应分别生成了铁(I)配合物Fe(PCP-Bu)(CO)和Fe(PCP-Bu)(CO)。文中提供了代表性配合物的X射线结构。
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