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An N-heterocyclic stannylene :Sn(NONAd) (NONAd = [O(SiMe2NAd)2]2−, Ad = 1-adamantyl), reacts rapidly with 2,4,6-tricyclohexylphenyl azide (TCHP)N3, affording a stannaimine, (NONAd)Sn＝N(TCHP). Solutions of (NONAd)Sn＝N(TCHP) react immediately with carbon dioxide (CO2) to give a [2+2]-cycloaddition product, which, upon heating, subsequently engages in a metathesis process to give [Sn(NONAd)(μ-O)]2 and the bulky isocyanate, (TCHP)NCO. [ABSTRACT FROM AUTHOR]

Reduction of the magnesium(II) diamide [Mg(TripNON)] (TripNON = 4,5-bis(2,4,6-triisopropylanilido)-2,7-diethyl-9,9-dimethyl-xanthene) with 5% w/w K/KI leads to a good yield of a dianionic dimagnesium(I) species, as its potassium salt, [{K(TripNON)Mg}2]. An X-ray crystallographic analysis shows the molecule to contain a very long Mg–Mg bond (3.137(2) Å). The formation of [{K(TripNON)Mg}2] contrasts with a previously reported reduction of a magnesium(II) complex incorporating a bulkier diamide ligand, which instead afforded a magnesium–dinitrogen complex. In the current study, [{K(TripNON)Mg}2] has been shown to be a viable reagent for the reductive activation of CO, H2 and N2O. [ABSTRACT FROM AUTHOR]

The reaction of compounds containing Al–Mg and Al–Zn bonds with N2O enabled isolation of the corresponding Al(μ-O)M complexes. Electronic structure analysis identified largely ionic Al–O and O–M bonds, featuring an anionic μ-oxo centre. Reaction with CO2 confirmed that these species correspond to the proposed intermediates in the formation of μ-carbonate compounds. [ABSTRACT FROM AUTHOR]

(NONDipp)Al–K(TMEDA)2 (NONDipp = [O(SiMe2NDipp)2]2−, Dipp = 2,6-iPr2C6H3), containing an Al–K bond, activates and reductively couples cabon monoxide gas to form the [C4O4]4− ligand. This oxocarbon anion is thermally isomerised in the presence of CO and TMEDA. In contrast, the dimeric potassium aluminyl [K{Al(NONDipp)}]2 yields an aluminium complex containing the hitherto unknown [C5O5]5− ligand. [ABSTRACT FROM AUTHOR]

We report the [Al(NONDipp)(Te)(THF)]− anion containing a terminal aluminium telluride bond. DFT calculations confirm appreciable Al–Te multiple bond character and reaction with CO2 proceeds via a double insertion to afford the previously unknown tellurodicarbonate ligand. [ABSTRACT FROM AUTHOR]