Department of Chemistry, University of Tromsø, N-9037 Tromsø, Norway.
Stanford Synchrotron Radiation Lightsource (SSRL), SLAC National Accelerator Laboratory, Stanford University, Menlo Park, California 94025, United States.
Inorg Chem. 2023 Jun 5;62(22):8467-8471. doi: 10.1021/acs.inorgchem.3c00632. Epub 2023 May 23.
The interaction of three free-base -tris(-X-phenyl)corroles H[TXPC] (X = H, CH, OCH) with Re(CO) at 235 °C in the presence of KCO in -dichlorobenzene has led to putative rhenium biscorrole sandwich compounds with the formula ReH[TXPC]. Density functional theory calculations and Re L-edge extended X-ray absorption fine structure measurements suggest a seven-coordinate metal center, with the "extra" hydrogen located on one of the corrole nitrogens. The complexes can be deprotonated by a base such as 1,8-diazabicyclo[5.4.0]undec-7-ene, resulting in a substantial sharpening of the UV-vis spectra and split Soret bands, consistent with the generation of -symmetric anions. Both the seven-coordinate neutral and eight-coordinate anionic forms of the complexes represent a new coordination motif in the field of rhenium-porphyrinoid interactions.
三种游离碱 -三（-X-苯基）corrole H[TXPC]（X = H，CH，OCH）与 Re(CO) 在 235°C 下，在 -二氯苯中存在 KCO 的条件下相互作用，导致了具有式 ReH[TXPC]的假定的铼双 corrole 夹心化合物。密度泛函理论计算和 Re L 边扩展 X 射线吸收精细结构测量表明，金属中心具有七配位，“额外”的氢位于 corrole 氮之一上。该配合物可以被碱如 1,8-二氮杂双环[5.4.0]十一碳-7-烯去质子化，导致 UV-vis 光谱和分裂的 Soret 带显著变窄，这与生成 -对称阴离子一致。配合物的七配位中性和八配位阴离子形式都代表了铼-卟啉相互作用领域中的一种新的配位模式。
