The potassium aluminyl complex K[Al(NON Ar )] (NON = NON Ar = [O(SiMe 2 NAr) 2 ] 2À ,A r = 2,6-iPr 2 C 6 H 3 ) reacts with 1,3,5,7-cyclooctatetraene (COT) to give K[Al-(NON Ar )(COT)].The COT-ligand is present in the asymmetric unit as ap lanar m 2 -h 2 :h 8 -bridge between Al and K, with additional K···p-aryl interactions to neighboring molecules that generate ah elical chain. DFT calculations indicate significant aromatic character,c onsistent with reduction to [COT] 2À . Addition of 18-crown-6c auses ar earrangement of the C 8carbocycle to form the isomeric 9-aluminabicyclo[4.2.1]nona-2,4,7-triene anion.

A seven‐membered N,N′‐heterocyclic potassium alumanyl nucleophile is introduced and utilised in the metathetical synthesis of Mg−Al and Ca−Al bonded derivatives. Both species have been characterised by experimental and theoretical means, allowing a rationalisation of the greater reactivity of the heavier group 2 species implied by an initial assay of their reactivity.

More than 80 years after Paneth's report of dimethyl bismuth, the first monomeric Bi(II) radical that is stable in the solid state has been isolated and characterized. Reduction of the diamidobismuth(III) chloride Bi(NON(Ar))Cl (NON(Ar)=[O(SiMe2NAr)2](2-); Ar=2,6-iPr2C6H3) with magnesium affords the Bi(II) radical ˙Bi(NON(Ar)). X-ray crystallographic measurements are consistent with a two-coordinate bismuth in the +2 oxidation state with no short intermolecular contacts, and solid-state SQUID magnetic measurements indicate a paramagnetic compound with a single unpaired electron. EPR and density functional calculations show a metal-centered radical with >90% spin density in a p-type orbital on bismuth.

Sodium reduction of [{SiN Dipp }Mg] [{SiN Dipp } = {CH 2 SiMe 2 N(Dipp)} 2 ; Dipp = 2,6-i-Pr 2 C 6 H 3 ] provides the Mg(I) species, [{SiN Dipp }MgNa] 2 , in which the long Mg−Mg bond (>3.2 Å) is augmented by persistent Na−aryl interactions. Computational assessment indicates that this molecule is best considered to comprise a contiguous tetrametallic core, a viewpoint borne out by its reaction with CO, which results in ethynediolate formation mediated by the dissimilar metal centers.

Bismuth diphenylphosphanides Bi(NON )(PPh ) (NON =[O(SiMe NR) ], R=tBu, 2,6-iPr C H , Aryl) undergo facile decomposition via single-electron processes to form reduced Bi and P species. The corresponding derivatives Bi(NON )(PCy ) are stable. Reaction of the isolated Bi radical Bi(NON ) with white phosphorus (P ) proceeds with the reversible and selective activation of a single P-P bond to afford the bimetallic μ,η -bicyclo[1.1.0]tetraphosphabutane compound.