Electronic and Structural Comparisons between Iron(II/III) and Ruthenium(II/III) Imide Analogs
作者:Kelly E. Aldrich、B. Scott Fales、Amrendra K. Singh、Richard J. Staples、Benjamin G. Levine、John McCracken、Milton R. Smith、Aaron L. Odom
DOI:10.1021/acs.inorgchem.9b01672
日期:2019.9.3
Ru(NAr/Ar*)(dmpe)2. A triphos ligand, P(Me)2CH2}3SitBu (tP3), was also examined. Addition of tP3 to Fe1 provided Fe(NAr)(tP3) (Fe4), but a similar reaction with Ru1 only gave intractable materials. Oxidation of Fe4 with AgSbF6 gave Fe(NAr)(tP3)}+SbF6– (Fe4a). Oxidation of Ru2 with AgSbF6 gave the unstable cation Ru(NAr)(PMe3)(dppe)}+, which dimerized in the presence of acetonitrile via C–C bond formation at the
为了检查亚铁和钌亚氨基配合物之间的结构和电子差异,制备了一系列具有不同膦基基础化合物的化合物。钌配合物的起始原料为Ru(NAr / Ar *)(PMe 3)3(Ru1 / Ru1 *),其中Ar = 2,6-(i Pr)2 C 6 H 3和Ar * = 2,4由顺式-RuCl 2(PMe 3)4和2当量的LiNHAr / Ar *制备的,6-(i Pr)3 C 6 H 2。铁络合物的起始原料是类似的Fe(NAr / Ar *)(PMe3)3种(Fe1 / Fe1 *),虽然不是孤立的,但可以从FeCl 2,PMe 3和LiNHAr / Ar *原位产生。在使用铁和钌的情况下,对PMe 3起始材料进行了膦螯合配体置换,得到了新的+2氧化态的8族亚氨基配合物。在M1 / M1 *中添加1,2-双(二苯基膦基)乙烷(dppe),得到Ru(NAr / Ar *)(PMe 3)(dppe)和Fe(NAr