Abstract: Rhodium(III) nitrate complexes trans-[(CH3)4N][Rh(H2O)2(NO3)4] (I), [(CH3)4N]Na2[Rh(H2O)6](NO3)6 (II), [(C2H5)4N]2[Rh(H2O)(NO3)5] (III) and [(CH3)4N]2[Rh(H2O)(NO3)5] (IV) were synthesized by the reactions of a “rhodium nitrate solution” with (CH3)4NNO3 and (C2H5)4NNO3. The complexes I, III and IV represent the first examples of soluble rhodium(III) complexes having four and five coordinated nitrato ligands, while II is the first example of a hexaaquarhodium(III) nitrate complex. Thermodynamic stability constants βi for the set of equilibria [Rh(H2O)6]3+ + iNO3􀀀 = [Rh(H2O)(6-i)(NO3)i](3􀀀 i) + iH2O were estimated using rhodium(III) solutions equilibrated for years. The constants decrease with the increase in the number of coordinated NO3􀀀 groups as follows: β1 ≈ 100, β2cis ≈ 10􀀀 1, β2trans ≈ 10􀀀 1 – 10􀀀 2, β3mer ≈ 10􀀀 2, β3fac ≈ 10􀀀 2, β4cis ≈ 10􀀀 4, β4trans ≈ 10􀀀 4. The kinetics and thermodynamics of NO3􀀀 ligands substitution with H2O molecules have been thoroughly studied by DFT calculations for a series of [Rh(NO3)x(H2O)6–x](3􀀀 x) complexes (x = 0–6). The high solubility of the synthesized complexes increases their synthetic significance and opens up new horizons in various practical applications such as homogeneous catalysis, photo- and electrochemistry, drug discovery and bioinorganic chemistry.

Cite: Vorobyeva S.N. , Shekhovtsov N.A. , Baidina I.A. , Sukhikh T.S. , Tkachev S.V. , Bushuev M.B. , Belyaev A.V.
The saga of rhodium(III) nitrate complexes and their speciation in solution: An integrated experimental and quantum chemical study
Polyhedron. 2022. V.211. P.115564. DOI: 10.1016/j.poly.2021.115564 WOS Scopus РИНЦ OpenAlex

Identifiers:

Web of science:	WOS:000719336700008
Scopus:	2-s2.0-85118892617
Elibrary:	47523562
OpenAlex:	W3214341829

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