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Interfragment transmission of electronic effects of π-acceptor ligands in heterometallic triad complexes with trans-[Ru(Py)4(CN)2] as a central unit

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Abstract

The complex trans-[RuPy4(CN)2] cleaves chloride bridges in the binuclear rhodium(i) and palladium(ii) complexes [Rh(CO)2Cl]2, [Rh(η4-C8H12)Cl]2, [(η4-C8H12)Rh(μ-Cl)2Rh(CO)2], [Pd(η3-C3H5)Cl]2, and [(η3-C3H5)Pd(μ-Cl)2Rh(CO)2] to form heterometallic triad complexes [(CO)2ClRh(NC)RuPy4(CN)RhCl(CO)2] (1), [(η4-C8H12)ClRh(NC)RuPy4(CN)RhCl-(η4-C8H12)] (2), [(CO)2ClRh(NC)RuPy4(CN)RhCl(η4-C8H12)] (3), [(η3-C3H5)ClPd(NC)-Ru(Py)4(CN)PdCl(η3-C3H5)] (4), and [(CO)2ClRh(NC)Ru(Py)4(CN)PdCl(η3-C3H5)] (5), respectively. In solutions, complex 3 coexists with equilibrium amounts of compounds 1 and 2; complex 5 is in the equilibrium with compounds 4 and 1. In both cases, the ratio of concentrations is close to binomial. Complexes 2 and 5 treated with [Rh(CO)2Cl]2 are converted into 1 with the simultaneous formation of [Rh(η4-C8H12)Cl]2 and [Pd(η3-C3H5)Cl]2, respectively. The δH and δC values for the ligands η4-C8H12, η3-C3H5, and CO are sensitive to the nature of the remote triad unit. The ligand effects are shown to be transmitted along the chain L′-M′-(NC)-Ru-(CN)-M″-L″.

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Authors and Affiliations

  1. Saint Petersburg State University, 26 Universitetsky prosp., 198504, Saint Petersburg, Russian Federation

    A. B. Nikol’skii, Yu. S. Varshavsky, T. G. Cherkasova, I. S. Podkorytov & V. A. Gindin

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  1. A. B. Nikol’skii
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  2. Yu. S. Varshavsky
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  3. T. G. Cherkasova
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  4. I. S. Podkorytov
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  5. V. A. Gindin
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Correspondence to Yu. S. Varshavsky.

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Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 4, pp. 0810–0817, April, 2012.

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Nikol’skii, A.B., Varshavsky, Y.S., Cherkasova, T.G. et al. Interfragment transmission of electronic effects of π-acceptor ligands in heterometallic triad complexes with trans-[Ru(Py)4(CN)2] as a central unit. Russ Chem Bull 61, 813–820 (2012). https://doi.org/10.1007/s11172-012-0113-7

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  • DOI: https://doi.org/10.1007/s11172-012-0113-7

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