In the presence of KOBut, N-heterocyclic
carbene-supported half-sandwich complex [Cp(IPr)Ru(pyr)2][PF6] (3) (IPr = 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene)
catalyzes transfer hydrogenation (TH) of nitriles, activated N-heterocycles, olefins, and conjugated olefins in isopropanol
at the catalyst loading of 0.5%. The TH of nitriles leads to imines,
produced as a result of coupling of the initially formed amines with
acetone (produced from isopropanol), and showed good chemoselectivity.
Reduction of N-heterocycles occurs for activated
polycyclic substrates (e.g., quinoline) and takes place exclusively
in the heterocycle. The TH also works well for linear and cyclic olefins
but fails for trisubstituted substrates. However, the CC bond
of α,β-unsaturated esters, amides, and acids is easily
reduced even for trisubstituted species, such as isovaleriates. Mechanistic
studies suggest that the active species in these catalytic reactions
is the trihydride Cp(IPr)RuH3 (5), which can
catalyze these reactions in the absence of any base. Kinetic studies
are consistent with a classical inner sphere hydride-based mechanism
of TH.
Bismuth molybdate catalysts have been used for partial oxidation and ammoxidation of light hydrocarbons since the 1950s. In particular, there is the synergy effect (the enhancement of the catalytic activity in the catalysts mixed from different components) in different phases of bismuth molybdate catalysts which has been observed and studied since the 1980s; however, despite it being interpreted differently by different research groups, there is still no decisive conclusion on the origin of the synergy effect that has been obtained. The starting idea of this work is to find an answer for the question: does the electrical conductivity influence the catalytic activity (which has been previously proposed by some authors). In this work, highly conductive materials (SnO 2 , ZrO 2 ) and nonconductive materials (MgO) are added to beta bismuth molybdates (β-Bi 2 Mo 2 O 9 ) using mechanical mixing, impregnation, and sol−gel methods. The mixtures were characterized by XRD, BET, XPS, and EDX techniques to determine the phase composition and surface properties. The conductivities of these samples were recorded at the catalytic reaction temperature (300−450 °C). Comparison of the catalytic activities of these mixtures showed that the addition of 10% mol SnO 2 to beta bismuth molybdate resulted in the highest activity while the addition of nonconductive MgO could not increase the catalytic activity. This shows that there may be a connection between conductivity and catalytic activity in the mixtures of bismuth molybdate catalysts and other metal oxides.
Reaction of complex [CpRu(pyr)3][PF6] (3) with the NHC carbene IPr (IPr = 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene) results in the NHC complex [Cp(IPr)Ru(pyr)2][PF6] (4), which was studied by NMR specroscopy and X-ray diffraction analysis. Reaction of [Cp(IPr)Ru(pyr)2][PF6] (4) with LiAlH4 leads to the trihydride Cp(IPr)RuH3 (5) characterised by spectroscopic methods. Heating compound 5 with hydrosilanes gives the dihydrido silyl derivatives Cp(IPr)RuH2(SiR3) (6). Systematic X-ray diffraction studies suggest that complexes 6 have stronger interligand Si∙∙∙H interactions than the isolobal phosphine complexes Cp(Pr3P)RuH2(SiR3).
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