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Papers by Arne Glüer

Research paper thumbnail of Iron catalyzed hydrogenation and electrochemical reduction of CO 2 : The role of functional ligands

Journal of Organometallic Chemistry, 2018

The reduction of CO2 is an attractive route to utilize the greenhouse gas as a C1 building block.... more The reduction of CO2 is an attractive route to utilize the greenhouse gas as a C1 building block. In recent years, the scientific progress that could be obtained for CO2 hydrogenation to formate and electrochemical reduction mainly to CO was strongly driven by the development of molecular iron catalysts with high activities and selectivities. However, these advances are also associated with the utilization of functional ligands that facilitate, e.g. H2 heterolysis in thermal hydrogenation or the storage of redox-equivalents in electrochemical transformations. In this review the use of such cooperating and redox non-innocent ligands in iron catalyzed CO2 transformations is discussed with the aim at providing some guidelines for catalyst design and improvement.

Research paper thumbnail of Hydrosilane Synthesis by Catalytic Hydrogenolysis of Chlorosilanes and Silyl Triflates

Inorganic Chemistry, 2018

Hydrogenolysis of the chlorosilanes and silyl triflates (triflate = trifluoromethanesulfonate, OT... more Hydrogenolysis of the chlorosilanes and silyl triflates (triflate = trifluoromethanesulfonate, OTf-) Me3-nSiX1+n (X = Cl, OTf; n = 0, 1) to hydrosilanes at mild conditions (4 bar H2, room temperature) is reported using low loadings (1 mol-%) of the bifunctional catalyst [Ru(H)2CO(HPNP iPr)] (HPNP iPr = HN(CH2CH2P(iPr)2)2). Endergonic chlorosilane hydrogenolysis can be driven by chloride removal, e.g. with NaBAr F 4 (BAr F 4-= B(C6H3-3,5-(CF3)2-). Alternatively, conversion to silyl triflates enables facile hydrogenolysis with NEt3 as base, giving Me3SiH, Me2SiH2 and Me2SiHOTf, respectively, in high yields. An outer-sphere mechanism for silyl triflate hydrogenolysis is supported by DFT computations. These protocols provide key steps for the synthesis of the valuable hydrochlorosilane Me2SiClH, which can also be directly obtained in yields over 50% by hydrogenolysis of chlorosilane/silyl triflate mixtures.

Research paper thumbnail of Highly Active Iron Catalyst for Ammonia Borane Dehydrocoupling at Room Temperature

ACS Catalysis, 2015

The iron complex [FeH(CO) (PNP)] (PNP = N(CH2CH2PiPr2)2) is a highly active catalyst for ammonia ... more The iron complex [FeH(CO) (PNP)] (PNP = N(CH2CH2PiPr2)2) is a highly active catalyst for ammonia borane dehydrocoupling at room temperature. Mainly linear polyaminoborane is obtained upon release of 1 equiv of H2. Mechanistic studies suggest that both hydrogen release and B–N coupling are metal-catalyzed and proceed via free aminoborane. Catalyst deactivation results from reaction with free BH3 that is formed by aminoborane rearrangement. Importantly, borane trapping with a simple amine allows for the observation of a TON that is unprecedented for a well-defined base metal catalyst.

Research paper thumbnail of Electron-rich, Nitrido-bridged Ruthenium Complexes

Zeitschrift für anorganische und allgemeine Chemie, 2014

Terminal RuIV nitride [RuN{N(CH2CH2PtBu2)2}] (1) and [RuCl{N(CH2CH2PtBu2)2}] (2a) form an equilib... more Terminal RuIV nitride [RuN{N(CH2CH2PtBu2)2}] (1) and [RuCl{N(CH2CH2PtBu2)2}] (2a) form an equilibrium with bridging nitride [{(tBu2PCH2CH2)2N}Ru(μ-N)RuCl{N(CH2CH2PtBu2)2}] (3a). While 3a could only be spectroscopically characterized yet not isolated, the reaction of the divinylamido chloro complex [RuCl{N(CHCHPtBu2)2}] (2b) with half an equivalent azide directly gave the analogous bridging nitride [{(tBu2PCHCH)2N}Ru(μ-N)RuCl{N(CHCHPtBu2)2}] (3b), which was isolated and fully characterized.

Research paper thumbnail of Iron catalyzed hydrogenation and electrochemical reduction of CO 2 : The role of functional ligands

Journal of Organometallic Chemistry, 2018

The reduction of CO2 is an attractive route to utilize the greenhouse gas as a C1 building block.... more The reduction of CO2 is an attractive route to utilize the greenhouse gas as a C1 building block. In recent years, the scientific progress that could be obtained for CO2 hydrogenation to formate and electrochemical reduction mainly to CO was strongly driven by the development of molecular iron catalysts with high activities and selectivities. However, these advances are also associated with the utilization of functional ligands that facilitate, e.g. H2 heterolysis in thermal hydrogenation or the storage of redox-equivalents in electrochemical transformations. In this review the use of such cooperating and redox non-innocent ligands in iron catalyzed CO2 transformations is discussed with the aim at providing some guidelines for catalyst design and improvement.

Research paper thumbnail of Hydrosilane Synthesis by Catalytic Hydrogenolysis of Chlorosilanes and Silyl Triflates

Inorganic Chemistry, 2018

Hydrogenolysis of the chlorosilanes and silyl triflates (triflate = trifluoromethanesulfonate, OT... more Hydrogenolysis of the chlorosilanes and silyl triflates (triflate = trifluoromethanesulfonate, OTf-) Me3-nSiX1+n (X = Cl, OTf; n = 0, 1) to hydrosilanes at mild conditions (4 bar H2, room temperature) is reported using low loadings (1 mol-%) of the bifunctional catalyst [Ru(H)2CO(HPNP iPr)] (HPNP iPr = HN(CH2CH2P(iPr)2)2). Endergonic chlorosilane hydrogenolysis can be driven by chloride removal, e.g. with NaBAr F 4 (BAr F 4-= B(C6H3-3,5-(CF3)2-). Alternatively, conversion to silyl triflates enables facile hydrogenolysis with NEt3 as base, giving Me3SiH, Me2SiH2 and Me2SiHOTf, respectively, in high yields. An outer-sphere mechanism for silyl triflate hydrogenolysis is supported by DFT computations. These protocols provide key steps for the synthesis of the valuable hydrochlorosilane Me2SiClH, which can also be directly obtained in yields over 50% by hydrogenolysis of chlorosilane/silyl triflate mixtures.

Research paper thumbnail of Highly Active Iron Catalyst for Ammonia Borane Dehydrocoupling at Room Temperature

ACS Catalysis, 2015

The iron complex [FeH(CO) (PNP)] (PNP = N(CH2CH2PiPr2)2) is a highly active catalyst for ammonia ... more The iron complex [FeH(CO) (PNP)] (PNP = N(CH2CH2PiPr2)2) is a highly active catalyst for ammonia borane dehydrocoupling at room temperature. Mainly linear polyaminoborane is obtained upon release of 1 equiv of H2. Mechanistic studies suggest that both hydrogen release and B–N coupling are metal-catalyzed and proceed via free aminoborane. Catalyst deactivation results from reaction with free BH3 that is formed by aminoborane rearrangement. Importantly, borane trapping with a simple amine allows for the observation of a TON that is unprecedented for a well-defined base metal catalyst.

Research paper thumbnail of Electron-rich, Nitrido-bridged Ruthenium Complexes

Zeitschrift für anorganische und allgemeine Chemie, 2014

Terminal RuIV nitride [RuN{N(CH2CH2PtBu2)2}] (1) and [RuCl{N(CH2CH2PtBu2)2}] (2a) form an equilib... more Terminal RuIV nitride [RuN{N(CH2CH2PtBu2)2}] (1) and [RuCl{N(CH2CH2PtBu2)2}] (2a) form an equilibrium with bridging nitride [{(tBu2PCH2CH2)2N}Ru(μ-N)RuCl{N(CH2CH2PtBu2)2}] (3a). While 3a could only be spectroscopically characterized yet not isolated, the reaction of the divinylamido chloro complex [RuCl{N(CHCHPtBu2)2}] (2b) with half an equivalent azide directly gave the analogous bridging nitride [{(tBu2PCHCH)2N}Ru(μ-N)RuCl{N(CHCHPtBu2)2}] (3b), which was isolated and fully characterized.

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