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Synthesis, Coordination Chemistry, and Cooperative Activation of H 2 with Ruthenium Complexes of Proton‐Responsive METAMORPhos Ligands
Author(s) -
Terrade Frédéric G.,
Lutz Martin,
van der Vlugt Jarl Ivar,
Reek Joost N. H.
Publication year - 2014
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.201301215
Subject(s) - chemistry , heterolysis , coordination sphere , coordination complex , triflic acid , ruthenium , phosphine , denticity , ligand (biochemistry) , adduct , chelation , tautomer , acetonitrile , stereochemistry , nuclear magnetic resonance spectroscopy , medicinal chemistry , crystallography , ion , inorganic chemistry , organic chemistry , crystal structure , catalysis , biochemistry , receptor , metal
The synthetic scope of proton‐responsive sulfonamidophosphorus (METAMORPhos) ligands is expanded and design principles for the selective formation of particular tautomers, ion pairs, or double condensation products are elucidated. These systems have been introduced in the coordination sphere of Ru for the first time, thereby enabling the exclusive coordination as a monoanionic P,O chelate. Depending on the Ru precursor, halide‐bridged dinuclear species 3 – 5 or cymene‐derived piano‐stool complexes 6 – 9 are isolated. The METAMORPhos framework is shown to play a role in the heterolytic cleavage of H 2 , with species 7 converted into neutral monohydride 10 . Substitution chemistry with cymene complex 7 has also been examined, thereby giving rise to tetrakis(acetonitrile) adduct 11 . Introduction of a second equivalent of METAMORPhos ligand to this species yielded the bis(ligated) derivative 13 , for which variable‐temperature (VT) NMR spectroscopy indicates coalescence of the phosphine donors at high temperature. Solid‐state structures of 3 , 6 , 11 , and 13 are presented to establish the precise bonding situation of the inorganic PNSO framework within METAMORPhos upon coordination as a proton‐responsive monoanionic P,O chelate.