Reduction of CO2 and Related Compounds with a Low‐Valent CaI Synthon
The reduction of CO2 with low‐valent s‐block metal complexes is limited to MgI reducing agents. Herein, the reduction of a series of CX2 reagents (X = O, S, NiPr) with the CaI synthon [(BDI)Ca(THP)]2(N2) (VI) is described, which is a CaII complex that reacts like the hypothetical CaI complex (BDI)Ca...
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| Language: | English |
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Wiley-VCH
2025-07-01
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| Series: | ChemistryEurope |
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| Online Access: | https://doi.org/10.1002/ceur.202500080 |
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| author | Stefan Thum Jonathan Mai Neha Patel Jens Langer Sjoerd Harder |
| author_facet | Stefan Thum Jonathan Mai Neha Patel Jens Langer Sjoerd Harder |
| author_sort | Stefan Thum |
| collection | DOAJ |
| description | The reduction of CO2 with low‐valent s‐block metal complexes is limited to MgI reducing agents. Herein, the reduction of a series of CX2 reagents (X = O, S, NiPr) with the CaI synthon [(BDI)Ca(THP)]2(N2) (VI) is described, which is a CaII complex that reacts like the hypothetical CaI complex (BDI)CaCa(BDI); BDI = HC[(Me)‐N(DIPeP)]2, DIPeP = 2,6‐Et2CH‐phenyl, THP = tetrahydropyran. Reaction of VI with excess CO2 led to crystallization of a carbonate complex with a Ca4(CO3)24+ core. The stabilizing BDI ligands also react by nucleophilic addition of CO2 at the backbone γ‐C atom. Reaction with only two equivalents of CO2 gave the presumed carbonite (CO22−) intermediate, but this could not be confirmed by X‐ray diffraction. Reaction with CS2 gave the first unique s‐block metal complex with a CS22− anion. This anion bridges between two (BDI)Ca+ cations by CaC and CaS bonding. The reduction of iPrN=C=NiPr with VI gave C–C coupling to a [(iPrN)2C–C(NiPr)2]2− dianion. An intermediate with a C(NiPr)22− dianion could not be isolated. |
| format | Article |
| id | doaj-art-c0b89b7a63024e0cbb1d004340b8f2bc |
| institution | Kabale University |
| issn | 2751-4765 |
| language | English |
| publishDate | 2025-07-01 |
| publisher | Wiley-VCH |
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| series | ChemistryEurope |
| spelling | doaj-art-c0b89b7a63024e0cbb1d004340b8f2bc2025-08-20T03:30:19ZengWiley-VCHChemistryEurope2751-47652025-07-0134n/an/a10.1002/ceur.202500080Reduction of CO2 and Related Compounds with a Low‐Valent CaI SynthonStefan Thum0Jonathan Mai1Neha Patel2Jens Langer3Sjoerd Harder4Inorganic and Organometallic Chemistry Friedrich‐Alexander Universität Erlangen‐Nürnberg Egerlandstraße 1 91058 Erlangen GermanyInorganic and Organometallic Chemistry Friedrich‐Alexander Universität Erlangen‐Nürnberg Egerlandstraße 1 91058 Erlangen GermanyInorganic and Organometallic Chemistry Friedrich‐Alexander Universität Erlangen‐Nürnberg Egerlandstraße 1 91058 Erlangen GermanyInorganic and Organometallic Chemistry Friedrich‐Alexander Universität Erlangen‐Nürnberg Egerlandstraße 1 91058 Erlangen GermanyInorganic and Organometallic Chemistry Friedrich‐Alexander Universität Erlangen‐Nürnberg Egerlandstraße 1 91058 Erlangen GermanyThe reduction of CO2 with low‐valent s‐block metal complexes is limited to MgI reducing agents. Herein, the reduction of a series of CX2 reagents (X = O, S, NiPr) with the CaI synthon [(BDI)Ca(THP)]2(N2) (VI) is described, which is a CaII complex that reacts like the hypothetical CaI complex (BDI)CaCa(BDI); BDI = HC[(Me)‐N(DIPeP)]2, DIPeP = 2,6‐Et2CH‐phenyl, THP = tetrahydropyran. Reaction of VI with excess CO2 led to crystallization of a carbonate complex with a Ca4(CO3)24+ core. The stabilizing BDI ligands also react by nucleophilic addition of CO2 at the backbone γ‐C atom. Reaction with only two equivalents of CO2 gave the presumed carbonite (CO22−) intermediate, but this could not be confirmed by X‐ray diffraction. Reaction with CS2 gave the first unique s‐block metal complex with a CS22− anion. This anion bridges between two (BDI)Ca+ cations by CaC and CaS bonding. The reduction of iPrN=C=NiPr with VI gave C–C coupling to a [(iPrN)2C–C(NiPr)2]2− dianion. An intermediate with a C(NiPr)22− dianion could not be isolated.https://doi.org/10.1002/ceur.202500080calciumcarbodiimideCO2CS2low‐valent |
| spellingShingle | Stefan Thum Jonathan Mai Neha Patel Jens Langer Sjoerd Harder Reduction of CO2 and Related Compounds with a Low‐Valent CaI Synthon ChemistryEurope calcium carbodiimide CO2 CS2 low‐valent |
| title | Reduction of CO2 and Related Compounds with a Low‐Valent CaI Synthon |
| title_full | Reduction of CO2 and Related Compounds with a Low‐Valent CaI Synthon |
| title_fullStr | Reduction of CO2 and Related Compounds with a Low‐Valent CaI Synthon |
| title_full_unstemmed | Reduction of CO2 and Related Compounds with a Low‐Valent CaI Synthon |
| title_short | Reduction of CO2 and Related Compounds with a Low‐Valent CaI Synthon |
| title_sort | reduction of co2 and related compounds with a low valent cai synthon |
| topic | calcium carbodiimide CO2 CS2 low‐valent |
| url | https://doi.org/10.1002/ceur.202500080 |
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