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Grishin ID, D'yachihin DI, Piskunov AV, et al. Carborane complexes of ruthenium(III): studies on thermal reaction chemistry and the catalyst design for atom transfer radical polymerization of methyl methacrylate. Inorg Chem. 2011;50(16):7574-85doi: 10.1021/ic200487w.
Grishin, I. D., D'yachihin, D. I., Piskunov, A. V., Dolgushin, F. M., Smol'yakov, A. F., Il'in, M. M., Davankov, V. A., Chizhevsky, I. T., & Grishin, D. F. (2011). Carborane complexes of ruthenium(III): studies on thermal reaction chemistry and the catalyst design for atom transfer radical polymerization of methyl methacrylate. Inorganic chemistry, 50(16), 7574-85. https://doi.org/10.1021/ic200487w
Grishin, Ivan D, et al. "Carborane complexes of ruthenium(III): studies on thermal reaction chemistry and the catalyst design for atom transfer radical polymerization of methyl methacrylate." Inorganic chemistry vol. 50,16 (2011): 7574-85. doi: https://doi.org/10.1021/ic200487w
Grishin ID, D'yachihin DI, Piskunov AV, Dolgushin FM, Smol'yakov AF, Il'in MM, Davankov VA, Chizhevsky IT, Grishin DF. Carborane complexes of ruthenium(III): studies on thermal reaction chemistry and the catalyst design for atom transfer radical polymerization of methyl methacrylate. Inorg Chem. 2011 Aug 15;50(16):7574-85. doi: 10.1021/ic200487w. Epub 2011 Jul 11. PMID: 21744846.
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Inorg Chem. 2011 Aug 15;50(16):7574-85. doi: 10.1021/ic200487w. Epub 2011 Jul 11.

Carborane complexes of ruthenium(III): studies on thermal reaction chemistry and the catalyst design for atom transfer radical polymerization of methyl methacrylate.

Inorganic chemistry

Ivan D Grishin, Dmitrii I D'yachihin, Alexander V Piskunov, Fedor M Dolgushin, Alexander F Smol'yakov, Mikhail M Il'in, Vadim A Davankov, Igor T Chizhevsky, Dmitry F Grishin

Affiliations

  1. Research Institute of Chemistry of the N. I. Lobachevsky Nizhny Novgorod State University, 23 Gagarin Avenue, Building 5, 603950 Nizhny Novgorod, Russian Federation.

PMID: 21744846 DOI: 10.1021/ic200487w

Abstract

The heating of the 18-electron complex [3,3-(dppb)-3-H-3-Cl-closo-3,1,2-RuC(2)B(9)H(11)] (3) in benzene at 80 °C in the presence of a small amount of CCl(4) as initiator afforded paramagnetic 17-electron species [3,3-(dppb)-3-Cl-closo-3,1,2-RuC(2)B(9)H(11)] (4) along with minor amounts of two P-phenylene ortho-cycloboronated derivatives [3-Cl-3,3,8-{Ph(2)P(CH(2))(4)PPh-μ-(C(6)H(4)-ortho)}-closo-3,1,2-RuC(2)B(9)H(10)] (5) and [3,7-Cl(2)-3,3,8-{Ph(2)P(CH(2))(4)PPh-μ-(C(6)H(4)-ortho)}-closo-3,1,2-RuC(2)B(9)H(10)] (6) in total yield of ca. 80%. The heating of either 3 or 4 in toluene at 95 °C in the absence of CCl(4) led to the selective formation of 5, which was isolated in 64% and 46% yield, respectively. Thermolysis of 3 at higher temperatures (boiling toluene, 110 °C) gives novel paramagnetic species [3-Cl-3,3,7,8-{Ph(2)P(CH(2))(4)P-μ-(C(6)H(4)-ortho)(2)}-closo-3,1,2-RuC(2)B(9)H(9)] (7) featuring bis(ortho-cycloboronation) of both P-phenyl groups at the same phosphorus atom of the ruthenium-bound dppb ligand. All new paramagnetic complexes 4-7, as well as starting diamagnetic species 3, were characterized by single-crystal X-ray diffraction and, in addition, by EPR spectroscopic studies of odd-electron complexes. Ruthenacarboranes 3-5 and 7 all display high efficiency as catalysts for the atom transfer radical polymerization (ATRP) of methyl methacrylate (MMA). Complex 5 gave the best catalyst performance in terms of polydispersity; the PDI (M(w)/M(n)) of the polymer samples is as low as 1.15.

© 2011 American Chemical Society

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