Tuning Ruthenium Carbene Complexes for Selective P−H Activation through Metal−Ligand Cooperation

Title	Tuning Ruthenium Carbene Complexes for Selective P−H Activation through Metal−Ligand Cooperation
Authors	Dr. Kai‐Stephan Feichtner, Dr. Lennart T. Scharf, Dr. Thorsten Scherpf, Dr. Bert Mallick, Nils Boysen, Prof. Dr. Viktoria H. Gessner
Magazine	Chemistry (Weinheim an Der Bergstrasse, Germany)
Date	11/11/2021
DOI	10.1002/chem.202103151
Introduction	The study investigates the activation of secondary phosphine P−H bonds using iminophosphoryl-tethered ruthenium carbene complexes. It reveals that complexes such as [(p-cymene)-RuC(SO2Ph)(PPh2NR)] exhibit varying reactivities based on the electronics of the phosphine and the iminophosphoryl moiety's substituent. Electron-rich silyl-substituted complexes can undergo cyclometallation or imine moiety shifts following P−H bond activation across the M=C linkage. Deuteration experiments and computational analyses demonstrate that cyclometallation begins with the M=C bond activation, spurred by high electron density at the metal in phosphido intermediates. Additionally, substituting trimethylsilyl with 4-nitrophenyl facilitates selective P−H activation, yielding stable products.
Quote	Kai‐Stephan Feichtner, Lennart T. Scharf and Thorsten Scherpf et al. Tuning Ruthenium Carbene Complexes for Selective P−H Activation through Metal‐Ligand Cooperation. Chemistry. 2021. DOI: 10.1002/chem.202103151
Element	Ruthenium (Ru) , Phosphorus (P) , Silicon (Si)
Materials	Chemical Compounds
Industry	Chemical & Pharmacy

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