Department of Chemistry, Brandeis University, 415 South Street, Waltham, MA, 02453, USA.
Angew Chem Int Ed Engl. 2018 Feb 5;57(6):1497-1500. doi: 10.1002/anie.201710100. Epub 2018 Jan 11.
Addition of H across the cobalt-phosphorus bond of (PPP)CoPMe (3) is demonstrated, where PPP is a monoanionic diphosphine pincer ligand with a central N-heterocyclic phosphido (NHP ) donor. The chlorophosphine Co complex (PP P)CoCl (2) can be generated through coordination of the chlorophosphine ligand (PP P, 1) to CoCl . Subsequent reduction of 2 with KC in the presence of PMe generates (PPP)CoPMe (3), in which both the phosphorus and cobalt centers have been reduced. The addition of 1 atm of H to complex 3 cleanly affords (PP P)Co(H)PMe (4), in which H has ultimately been added across the metal-phosphorus bond. Complex 4 was characterized spectroscopically and using computational methods to predict its geometry.
添加 H 跨越钴-磷键的（PPP）CoPMe（3），其中 PPP 是一种带有中央 N-杂环膦基（NHP）供体的单阴离子双膦钳配体。氯膦基 Co 配合物（PPP）CoCl（2）可以通过氯膦配体（PPP，1）与 CoCl 的配位生成。随后，在 PMe 的存在下用 KC 将 2 还原，生成（PPP）CoPMe（3），其中磷和钴中心都已被还原。将 1 atm 的 H 添加到配合物 3 中可得到（PPP）Co（H）PMe（4），其中 H 最终已添加到金属-磷键上。通过光谱和计算方法对配合物 4 进行了表征，以预测其几何形状。
