Barrett Brittany J, Iluc Vlad M
Department of Chemistry and Biochemistry, University of Notre Dame , 251 Nieuwland Science Hall, Notre Dame, Indiana 46556, United States.
Inorg Chem. 2014 Jul 21;53(14):7248-59. doi: 10.1021/ic500549z. Epub 2014 Jun 24.
The coordination chemistry of a neutral tPCH═CHP pincer (tPCH═CHP = 2,2'-bis(di-iso-propylphosphino)-trans-stilbene) with metals that form stable complexes in the +1 oxidation state was studied and (tPCH═CHP)CoCl, (tPCH═CHP)CoCl(CO), (tPCH═CHP)RhCl, (tPCH═CHP)Cu(OTf), [(tPCH═CHP)Cu][PF6], and [(tPCH═CHP)Ag][PF6] were synthesized and characterized. In order to determine whether the coordination mode is dependent on the oxidation state of the metal, some +2 metal complexes, (tPCH═CHP)CoCl2 and (tPCH═CHP)FeBr2, were also investigated. The coordination of the olefinic backbone is not observed in (tPCH═CHP)FeBr2, (tPCH═CHP)CoCl2, (tPCH═CHP)Cu(OTf), or [(tPCH═CHP)Ag][PF6], but η(2)-coordination is present in [(tPCH═CHP)CoCl][BAr(F)4], [(tPCH═CHP)FeBr][BAr(F)4], (tPCH═CHP)CoCl, (tPCH═CHP)CoCl(CO), (tPCH═CHP)RhCl, and [(tPCH═CHP)Cu][PF6]. Cobalt(II), iron(II), and copper(I) formed complexes with the ligand in both coordination modes. All metal complexes were characterized by multinuclei NMR spectroscopy, X-ray crystallography, and elemental analysis.
研究了一种中性的tPCH═CHP钳形配体（tPCH═CHP = 2,2'-双（二异丙基膦基）-反式芪）与在 +1 氧化态下形成稳定配合物的金属的配位化学，并合成和表征了(tPCH═CHP)CoCl、(tPCH═CHP)CoCl(CO)、(tPCH═CHP)RhCl、(tPCH═CHP)Cu(OTf)、[(tPCH═CHP)Cu][PF6] 和 [(tPCH═CHP)Ag][PF6]。为了确定配位模式是否取决于金属的氧化态，还研究了一些 +2 价金属配合物 (tPCH═CHP)CoCl2 和 (tPCH═CHP)FeBr2。在 (tPCH═CHP)FeBr2、(tPCH═CHP)CoCl2、(tPCH═CHP)Cu(OTf) 或 [(tPCH═CHP)Ag][PF6] 中未观察到烯烃主链的配位，但在 [(tPCH═CHP)CoCl][BAr(F)4]、[(tPCH═CHP)FeBr][BAr(F)4]、(tPCH═CHP)CoCl、(tPCH═CHP)CoCl(CO)、(tPCH═CHP)RhCl 和 [(tPCH═CHP)Cu][PF6] 中存在 η(2)-配位。钴 (II)、铁 (II) 和铜 (I) 以两种配位模式与配体形成配合物。所有金属配合物均通过多核 NMR 光谱、X 射线晶体学和元素分析进行了表征。
