Dinitrogen Cleavage and Functionalization with Carbon Dioxide in a Dititanium Dihydride Framework
- Qingde ZhuoQingde ZhuoOrganometallic Chemistry Laboratory, RIKEN Cluster for Pioneering Research, 2-1 Hirosawa, Wako, Saitama 351-0198, JapanMore by Qingde Zhuo
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- Jimin YangJimin YangState Key Laboratory of Fine Chemicals, School of Chemical Engineering, Dalian University of Technology, Dalian 116024, ChinaMore by Jimin Yang
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- Zhenbo MoZhenbo MoOrganometallic Chemistry Laboratory, RIKEN Cluster for Pioneering Research, 2-1 Hirosawa, Wako, Saitama 351-0198, JapanMore by Zhenbo Mo
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- Xiaoxi ZhouXiaoxi ZhouOrganometallic Chemistry Laboratory, RIKEN Cluster for Pioneering Research, 2-1 Hirosawa, Wako, Saitama 351-0198, JapanMore by Xiaoxi Zhou
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- Takanori ShimaTakanori ShimaOrganometallic Chemistry Laboratory, RIKEN Cluster for Pioneering Research, 2-1 Hirosawa, Wako, Saitama 351-0198, JapanAdvanced Catalysis Research Group, RIKEN Center for Sustainable Resource Science, 2-1 Hirosawa, Wako, Saitama 351-0198, JapanMore by Takanori Shima
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- Yi Luo*Yi Luo*Email: [email protected]State Key Laboratory of Fine Chemicals, School of Chemical Engineering, Dalian University of Technology, Dalian 116024, ChinaPetroChina Petrochemical Research Institute, Beijing 102206, ChinaMore by Yi Luo
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- Zhaomin Hou*Zhaomin Hou*Email: [email protected]Organometallic Chemistry Laboratory, RIKEN Cluster for Pioneering Research, 2-1 Hirosawa, Wako, Saitama 351-0198, JapanAdvanced Catalysis Research Group, RIKEN Center for Sustainable Resource Science, 2-1 Hirosawa, Wako, Saitama 351-0198, JapanMore by Zhaomin Hou
Abstract
The activation and functionalization of dinitrogen (N2) with carbon dioxide (CO2) are of great interest and importance but highly challenging. We report here for the first time the reaction of N2 with CO2 in a dititanium dihydride framework, which leads to N–C bond formation and N–N and C–O bond cleavage. Exposure of a dinitrogen dititanium hydride complex {[(acriPNP)Ti]2(μ2-η1:η2-N2)(μ2-H)2} (1) (acriPNP = 4,5-bis(diisopropylphosphino)-2,7,9,9-tetramethyl-9H-acridin-10-ide) to a CO2 atmosphere at room temperature rapidly yielded a nitrido/N,N-dicarboxylamido complex {[(acriPNP)Ti]2(μ2-N)[μ2-N(CO2)2]} (2, 28%) and a diisocyanato/dioxo complex {[(acriPNP)Ti]2(NCO)2(μ2-O)2} (3, 52%) with release of H2. When the reaction of 1 with CO2 (1 atm) was carried out at −50 °C, complex 2 was selectively formed in 82% yield within 5 min. Heating 2 at 80 °C under 1 atm CO2 for 30 min afforded 3 in 67% yield. When 1 was allowed to react with 1.5 equiv of CO2 at room temperature, an isocyanato/nitrido/oxo complex {[(acriPNP)Ti]2(NCO)(μ2-N)(μ2-O)} (4) was exclusively formed in 89% yield within 5 min. The reaction of 4 with CO2 at room temperature almost quantitatively yielded the dioxo/diisocyanato complex 3 within 5 min. The mechanistic details were clarified by the 15N- and 13C-labeled experiments and density functional theory (DFT) calculations, providing unprecedented insights into the reaction of N2 with CO2. A titanium-mediated cycle for the synthesis of trimethylsilyl isocyanate Me3SiNCO from N2, CO2, and Me3SiCl using H2 as a reducing agent was also established.
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