Nitroxyl as a ligand in ruthenium tetraammine systems: a density functional theory study

Dalton Transactions : an International Journal of Inorganic Chemistry
Augusto C H Da SilvaDouglas W Franco

Abstract

The properties of the free nitroxyl molecule and the nitroxyl ligand in Ru(ii) tetraammines (trans-[Ru(NH3)4(nitroxyl)(n)(L)](2+n) (n = nitroxyl charge; L = NH3, py, P(OEt)3, H2O, Cl(-) and Br(-))) were studied using density functional theory. According to the calculated conformational energies, HNO complexes are more stable than their deprotonated analogues, and the singlet configuration (trans-(1)[Ru(NH3)4(L)HNO](2+)) is lower in energy than the corresponding triplet (trans-(3)[Ru(NH3)4(L)HNO](2+)). An evaluation of the σ and π components of the L-Ru-HNO bond suggest that the increased stability of these orbitals and the enhanced contributions from the HNO orbitals correlate to shorter Ru-N(H)O distances and higher νRu-HNO stretching frequencies. The stability of the Ru-HNO bond was also evaluated through a theoretical kinetic study of HNO dissociation from trans-(1)[Ru(NH3)4(L)HNO](2+). The order of the Ru-HNO bonding stability in trans-(1)[Ru(NH3)4(L)HNO](2+) as a function of L was found to be as follows: H2O > Cl(-)∼ Br(-) > NH3 > py > P(OEt)3. This order parallels the order of the trans-effect and trans-influence series experimentally measured for L in octahedral complexes. The same trend was also observed using an explic...Continue Reading

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Citations

Feb 18, 2017·Journal of Computational Chemistry·Renato Pereira OrenhaSérgio Emanuel Galembeck
Dec 12, 2017·Journal of the American Chemical Society·Lauren M LoftusClaudia Turro

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