Department of Chemistry and Chemical Biology, Harvard University, Cambridge, MA 02138, USA.
Acta Crystallogr C Struct Chem. 2021 Mar 1;77(Pt 3):161-166. doi: 10.1107/S2053229621001388. Epub 2021 Feb 26.
The dichromium Pacman complex (dmx)CrCl·CHO (1) [(dmx)H is a dimethylxanthene-bridged cofacial (bis)dipyrrin, CHNO] was synthesized by salt metathesis using anhydrous CrCl and previously reported (dmx)K. Treatment of 1 with two equivalents of the reductant potassium graphite afforded K(dmx)CrCl(thf)·0.5CHO·0.5CHO (thf is tetrahydrofuran, CHO) (2), with both potassium ions intercalated between the pyrrolic subunits. Comparison of the solid-state structures for 1 and 2 reveals minimal changes in the primary coordination sphere of each Cr ion, with notable elongation of the dipyrrin C-C and C-N bonds upon reduction, consistent with computational support for a ligand-based reduction.
二铬方糖复合物（dmx）CrCl·CHO（1）[（dmx）H 是二甲氧芴桥联的面对面（双）二吡咯，CHNO]通过使用无水 CrCl 和先前报道的（dmx）K 的盐复分解合成。用两倍当量的还原剂钾石墨处理 1 得到 K（dmx）CrCl（thf）·0.5CHO·0.5CHO（thf 是四氢呋喃，CHO）（2），两个钾离子插在吡咯亚基之间。1 和 2 的固态结构比较表明每个 Cr 离子的第一配位层变化很小，还原后二吡咯的 C-C 和 C-N 键显著伸长，与基于配体的还原的计算支持一致。
