Picolyl–NHC Hydrotris(pyrazolyl)borate Ruthenium(II) Complexes: Synthesis, Characterization, and Reactivity with Small Molecules | Zendy

Francys E. Fernández | Zendy; M.C. Puerta | Zendy; Pedro Valerga | Zendy

Open Access

Picolyl–NHC Hydrotris(pyrazolyl)borate Ruthenium(II) Complexes: Synthesis, Characterization, and Reactivity with Small Molecules

Author(s) -

Francys E. Fernández,

M.C. Puerta,

Pedro Valerga

Publication year - 2013

Publication title -

inorganic chemistry

Language(s) - English

Resource type - Journals

SCImago Journal Rank - 1.348

H-Index - 233

eISSN - 1520-510X

pISSN - 0020-1669

DOI - 10.1021/ic302553z

Subject(s) - chemistry , ruthenium , reactivity (psychology) , boron , characterization (materials science) , molecule , polymer chemistry , medicinal chemistry , combinatorial chemistry , organic chemistry , catalysis , nanotechnology , medicine , alternative medicine , pathology , materials science

Ruthenium(II) hydrotris(pyrazolyl)borate chloro complexes bearing picolyl-functionalized N-heterocyclic carbenes [TpRu(κ(2)-C,N-picolyl-(R)I)Cl] (picolyl-(Me)I = 3-methyl-1-(2-picolyl)imidazol-2-ylidene) (1a), picolyl-(iPr)I = 3-isopropyl-1-(2-picolyl)imidazol-2-ylidene (1b), picolyl-(Me)45DClI = 3-methyl-1-(2-picolyl)-4,5-dichloroimidazol-2-ylidene (1c), picolyl-(Ph)I = 3-phenyl-1-(2-picolyl)imidazol-2-ylidene (1d), picolyl-(Me)BI = 3-methyl-1-(2-picolyl)benzoimidazol-2-ylidene (1e)) have been synthesized and characterized. Furthermore, cationic carbonyl derivatives 2a-e have been prepared, characterized, and used to study the donor properties of the picolylcarbene ligands (picolyl-(R)I) via infrared spectroscopy. Also, the reactivity of the 16-electron species [TpRu(κ(2)-C,N-picolyl-(R)I)](+), in situ generated using NaBAr(F)4 (Ar(F) = 3,5-bis(trifluoromethyl)phenyl) as a halide scavenger, toward N2, CH3CN, H2, CH2CH2, S8, and O2 was studied indicating a strong influence of the NHC wingtip and backbone substituents in the product distribution. The crystal structures of [TpRu(κ(2)-C,N-picolyl-(iPr)I)Cl] (1b), [TpRu(κ(2)-C,N-picolyl-(Me)I)CO][BAr(F)4] (2a), [TpRu(κ(2)-C,N-picolyl-(Ph)I)CO][BAr(F)4] (2d), [{TpRu(κ(2)-C,N-picolyl-(Me)I}2(μ-N2)][BAr(F)4]2 (3'a), [{TpRu(κ(2)-C,N-picolyl-(Ph)I)}2(μ-N2)][BAr(F)4]2 (3'd), [TpRu(κ(2)-C,N-picolyl-(iPr)I)(η(2)-CH2CH2)][BAr(F)4] (5b), and [{TpRu(κ(2)-C,N-picolyl-(Me)I)}2(μ-S2)][BAr(F)4]2 (6) are reported.

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