4.8 Article

An Aluminum Telluride with a Terminal Al=Te Bond and its Conversion to an Aluminum Tellurocarbonate by CO2 Reduction

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WILEY-V C H VERLAG GMBH
DOI: 10.1002/anie.202216021

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Aluminum Selenide; Aluminum Telluride; CO2 Activation; Chalcogen; Tellurocarbonate

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Facile access to dimeric heavier aluminum chalcogenides [(NHC)Al(Tipp)-mu-Ch](2) (NHC=IiPr, IMe4; Tipp=2,4,6-iPr(3)C(6)H(2); Ch=Se, Te) by treatment of NHC-stabilized aluminum dihydrides with elemental Se and Te is reported. The higher affinity of IMe4 in comparison with IiPr toward the Al center in [(NHC)Al(Tipp)-mu-Ch](2) can be used for ligand exchange. Additionally, the presence of excess IMe4 allows for cleavage of the dimers to form a rare example of a neutral multiply bonded heavier aluminum chalcogenide in the form of a tetracoordinate aluminum complex, (IMe4)(2)(Tipp)Al=Te. This species reacts with three equivalents of CO2 across two Al-C-NHC and the Al=Te bond affording a pentacoordinate aluminum complex containing a dianionic tellurocarbonate ligand [CO2Te](2-), which is the first example of tellurium analogue of a carbonate [CO3](2-).
Facile access to dimeric heavier aluminum chalcogenides [(NHC)Al(Tipp)-mu-Ch](2) (NHC=IiPr (1,3-diisopropyl-4,5-dimethylimidazol-2-ylidene, IMe4 (1,3,4,5-tetramethylimidazol-2-ylidene); Tipp=2,4,6-iPr(3)C(6)H(2); Ch=Se, Te) by treatment of NHC-stabilized aluminum dihydrides with elemental Se and Te is reported. The higher affinity of IMe4 in comparison with IiPr toward the Al center in [(NHC)Al(Tipp)-mu-Ch](2) can be used for ligand exchange. Additionally, the presence of excess IMe4 allows for cleavage of the dimers to form a rare example of a neutral multiply bonded heavier aluminum chalcogenide in the form of a tetracoordinate aluminum complex, (IMe4)(2)(Tipp)Al=Te. This species reacts with three equivalents of CO2 across two Al-C-NHC and the Al=Te bond affording a pentacoordinate aluminum complex containing a dianionic tellurocarbonate ligand [CO2Te](2-), which is the first example of tellurium analogue of a carbonate [CO3](2-).

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