New RuII(arene) Complexes with Halogen-Substituted Bis- and Tris(pyrazol-1-yl)borate Ligands

[RuCl(arene)(μ‐Cl)]2 dimers were treated in a 1:2 molar ratio with sodium or thallium salts of bis‐ and tris(pyrazolyl)borate ligands [Na(Bp Br 3)], [Tl(Tp Br 3)], and [Tl(TpiPr, 4Br)]. Mononuclear neutral complexes [RuCl(arene)(κ2‐Bp Br 3)] (1: arene=p‐cymene (cym); 2: arene=hexamethylbenzene (hmb); 3: arene=benzene (bz)), [RuCl(arene)(κ2‐Tp Br 3)] (4: arene=cym; 6: arene=bz), and [RuCl(arene)(κ2‐TpiPr, 4Br)] (7: arene=cym, 8: arene=hmb, 9: arene=bz) have been always obtained with the exception of the ionic [Ru2(hmb)2(μ‐Cl)3][Tp Br 3] (5′), which formed independently of the ratio of reactants and reaction conditions employed. The ionic [Ru(CH3OH)(cym)(κ2‐Bp Br 3)][X] (10: X=PF6, 12: X=O3SCF3) and the neutral [Ru(O2CCF3)(cym)(κ2‐Bp Br 3)] (11) have been obtained by a metathesis reaction with corresponding silver salts. All complexes 1–12 have been characterized by analytical and spectroscopic data (IR, ESI‐MS, 1H and 13C NMR spectroscopy). The structures of the thallium and calcium derivatives of ligand Tp Br 3, [Tl(Tp Br 3)] and [Ca(dmso)6][Tp Br 3]2⋅2 DMSO, of the complexes 1, 4, 5′, 6, 11, and of the decomposition product [RuCl(cym)(HpziPr, 4Br)2][Cl] (7′) have been confirmed by using single‐crystal X‐ray diffraction. Electrochemical studies showed that 1–9 and 11 undergo a single‐electron RuII→RuIII oxidation at a potential, measured by cyclic voltammetry, which allows comparison of the electron‐donor characters of the bis‐ and tris(pyrazol‐1‐yl)borate and arene ligands, and to estimate, for the first time, the values of the Lever EL ligand parameter for Bp Br 3, Tp Br 3, and TpiPr, 4Br. Theoretical calculations at the DFT level indicated that both oxidation and reduction of the Ru complexes under study are mostly metal‐centered with some involvement of the chloride ligand in the former case, and also demonstrated that the experimental isolation of the μ3‐binuclear complex 5′ (instead of the mononuclear 5) is accounted for by the low thermodynamic stability of the latter species due to steric reasons. Fine tuning: A combination of steric and electronic features of bromine‐substituted scorpionate ligands and an arene moiety has provided an unexpected μ3‐binuclear ionic complex instead of the mononuclear neutral one; this is accounted for by the low thermodynamic stability of the latter species. The coordination chemistry of RuII(arene) toward Tpx ligands was analyzed using X‐ray diffraction (see figure), electrochemical and DFT methods.