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Density Functional Theory (DFT)-based bonding analysis correlates ligand field strength with $$^{99}$$Ru M$"o$ssbauer parameters of ruthenium-nitrosyl complexes

Kaneko, Masashi ; Kato, Akane*; Nakashima, Satoru*; Kitatsuji, Yoshihiro

We applied density functional theory calculations to ruthenium-nitrosyl complexes, which are known to exist in high-level radioactive waste, to give a theoretical correlation between $$^{99}$$Ru M$"o$ssbauer spectroscopic parameters ($$delta$$ and $$Delta$$$$E_{rm Q}$$) and ligand field strength ($$Delta$$$$_{rm o}$$) for the first time. The structures of the series of complexes, [Ru(NO)L$$_{5}$$] (L = Br$$^{-}$$, Cl$$^{-}$$, NH$$_{3}$$, CN$$^{-}$$), were modeled based on the corresponding single-crystal X-ray coordinates. The comparisons of the geometries and total energies between the different spin states suggested that the singlet spin state of [Ru(II)(NO$$^{+}$$)L$$_{5}$$] complexes were the most stable. The calculated results of both the $$delta$$ and $$Delta$$$$E_{rm Q}$$ values reproduced the experimental results by reported previously and increased in the order of L = Br$$^{-}$$, Cl$$^{-}$$, NH$$_{3}$$, CN$$^{-}$$. Finally, we estimated the ligand field strength ($$Delta$$$$_{rm o}$$) based on molecular orbitals, assuming C$$_{rm 4v}$$ symmetry and showed the increase of $$Delta$$$$_{rm o}$$ values in that order, being consistent with well-known spectrochemical series of ligands. The increase attributes to the strengthening of the abilities of $$sigma$$-donor and $$pi$$-acceptor of the L-ligands to the Ru atom, resulting in the increase of the $$delta$$ values.



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Category:Chemistry, Inorganic & Nuclear



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