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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| Main Authors: | , , , , |
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| Format: | Article |
| Language: | English |
| Published: |
Wiley-VCH
2025-07-01
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| Series: | ChemistryEurope |
| Subjects: | |
| Online Access: | https://doi.org/10.1002/ceur.202500080 |
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| Summary: | 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. |
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| ISSN: | 2751-4765 |