UCSD-CNRS Joint Research Laboratory (UMI 3555), Department of Chemistry and Biochemistry, University of California, San Diego , La Jolla, California 92093-0358, United States.
J Am Chem Soc. 2016 Dec 14;138(49):15885-15888. doi: 10.1021/jacs.6b11496. Epub 2016 Dec 2.
(Phosphino)phosphaketenes (>P-P═C═O) behave as (phosphino)phosphinidene-carbonyl adducts (>P-P←:C═O). CO scrambling was observed using C labeled CO, and exchange reactions with phosphines afford the corresponding (phosphino)phosphinidene-phosphine adducts (>P-P←:PR). The latter react with isonitriles and singlet carbenes giving (phosphino)phosphinidene-isonitrile (>P-P←:CNR) and -carbene adducts (>P-P←:C<). Based on experimental results and DFT calculations, it is shown that these "ligand" exchange reactions occur via an associative mechanism as classically observed with transition metal complexes.
(膦基)亚膦烯 (>P-P═C═O) 表现为 (膦基)亚膦烯-羰基加合物 (>P-P←:C═O)。使用 C 标记的 CO 观察到 CO 重排，与膦的交换反应得到相应的 (膦基)亚膦烯-膦加合物 (>P-P←:PR)。后者与异腈和单重卡宾反应，生成 (膦基)亚膦烯-异腈 (>P-P←:CNR) 和 -卡宾加合物 (>P-P←:C<)。基于实验结果和 DFT 计算，表明这些“配体”交换反应通过经典观察到的过渡金属配合物的缔合机制发生。
