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Electronic Communication in Binuclear Osmium- and Iridium-Polyhydrides.

Lara CancelaMiguel A EsteruelasJavier GalbánMontserrat OlivánEnrique OñateAndrea VélezJuan C Vidal
Published in: Inorganic chemistry (2021)
Reactions of polyhydrides OsH6(PiPr3)2 (1) and IrH5(PiPr3)2 (2) with rollover cyclometalated hydride complexes have been investigated in order to explore the influence of a metal center on the MHn unit of the other in mixed valence binuclear polyhydrides. Hexahydride 1 activates an ortho-CH bond of the heterocyclic moiety of the trihydride metal-ligand compounds OsH3{κ2-C,N-[C5RH2N-py]}(PiPr3)2 (R = H (3), Me (4), Ph (5)). Reactions of 3 and 4 lead to the hexahydrides (PiPr3)2H3Os{μ-[κ2-C,N-[C5RH2N-C5H3N]-N,C-κ2]}OsH3(PiPr3)2 (R = H (6), Me (7)), whereas 5 gives the pentahydride (PiPr3)2H3Os{μ-[κ2-C,N-[C5H3N-C5(C6H4)H2N]-C,N,C-κ3]}OsH2(PiPr3)2 (8). Pentahydride 2 promotes C-H bond activation of 3 and the iridium-dihydride IrH2{κ2-C,N-[C5H3N-py]}(PiPr3)2 (9) to afford the heterobinuclear pentahydride (PiPr3)2H3Os{μ-[κ2-C,N-[C5H3N-C5H3N]-N,C-κ2]}IrH2(PiPr3)2 (10) and the homobinuclear tetrahydride (PiPr3)2H2Ir{μ-[κ2-C,N-[C5H3N-C5H3N]-N,C-κ2]}IrH2(PiPr3)2 (11), respectively. Complexes 6-8 and 11 display HOMO delocalization throughout the metal-heterocycle-metal skeleton. Their sequential oxidation generates mono- and diradicals, which exhibit intervalence charge transfer transitions. This notable ability allows the tuning of the strength of the hydrogen-hydrogen and metal-hydrogen interactions within the MHn units.
Keyphrases
  • hydrogen peroxide
  • mass spectrometry
  • nitric oxide
  • visible light
  • high resolution
  • single molecule
  • transition metal