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

Abstract The potassium aluminyl complex K[Al(NON Ar )] (NON=NON =[O(SiMe 2 NAr) ] 2− , Ar=2,6‐ i Pr C 6 H 3 ) reacts with 1,3,5,7‐cyclooctatetraene (COT) to give )(COT)]. COT‐ligand is present in the asymmetric unit as a planar μ ‐η :η 8 ‐bridge between Al and K, additional K⋅⋅⋅π‐aryl interactions neighboring molecules that generate helical chain. DFT calculations indicate significant aromatic character, consistent reduction [COT] . Addition of 18‐crown‐6 causes rearrangement ‐carbocycle...

Abstract More than 80 years after Paneth’s report of dimethyl bismuth, the first monomeric Bi II radical that is stable in solid state has been isolated and characterized. Reduction diamidobismuth(III) chloride Bi(NON Ar )Cl (NON =[O(SiMe 2 NAr) ] 2− ; Ar=2,6‐ i Pr C 6 H 3 ) with magnesium affords . ). X‐ray crystallographic measurements are consistent a two‐coordinate bismuth +2 oxidation no short intermolecular contacts, solid‐state SQUID magnetic indicate paramagnetic compound single...

A seven-membered N,N'-heterocyclic potassium alumanyl nucleophile is introduced and utilised in the metathetical synthesis of Mg-Al Ca-Al bonded derivatives. Both species have been characterised by experimental theoretical means, allowing a rationalisation greater reactivity heavier group 2 implied an initial assay their reactivity.Al‐Ca‐Wrap: Die Reaktion eines siebengliedrigen cyclischen Alumanyl‐Anions mit einem β‐Diketiminato‐Calciumtetraphenylborat bietet einen leichten Zugang zu...

Abstract Copper‐alumanyl complexes, [LCu‐Al(SiN Dipp )], where L=carbene=NHC iPr (N,N′‐diisopropyl‐4,5‐dimethyl‐2‐ylidene) and Me2 CAAC (1‐(2,6‐diisopropylphenyl)‐3,3,5,5‐tetramethyl‐pyrrolidin‐2‐ylidene) featuring unsupported Al−Cu bonds, have been prepared. Divergent reactivity observed with carbodiimides CO 2 implies an ambiphilicity in the Cu–Al interaction that is dependent on identity of carbene co‐ligand.

Bismuth diphenylphosphanides Bi(NONR )(PPh2 ) (NONR =[O(SiMe2 NR)2 ], R=tBu, 2,6-iPr2 C6 H3 , Aryl) undergo facile decomposition via single-electron processes to form reduced Bi and P species. The corresponding derivatives )(PCy2 are stable. Reaction of the isolated BiII radical . Bi(NONAr with white phosphorus (P4 proceeds reversible selective activation a single P-P bond afford bimetallic μ,η1:1 -bicyclo[1.1.0]tetraphosphabutane compound.

The reaction of the potassium aluminyl K[Al(NONDipp)] (NONDipp = [O(SiMe2NDipp)2]2-, Dipp 2,6-iPr2C6H3) with an organic azide generates aluminium imide complex, K[Al(NONDipp)(NMes)] (Mes mesityl 2,4,6-Me3C6H2). DFT calculations indicate Al-Nimide interaction is polarized but has appreciable multiple-bond character. This demonstrated experimentally by carbon dioxide, giving a rare example main group carbamate dianion via [2+2] cycloaddition reaction.

Bismuth(iii) TEMPOxide compounds have been synthesized from the coupling of Bi(ii) species with TEMPO˙ radical. The steric profile supporting bis(amido)disiloxane ligand promotes different fluxional behaviour in solution, and DFT calculations suggest variation Bi-O bond character. These are active catalysts for oxidative TEMPO silane substrates, believed to proceed via metathesis Si-H bonds followed by decomposition bismuth-hydride intermediate species.

Sodium reduction of [{SiNDipp}Mg] [{SiNDipp} = {CH2SiMe2N(Dipp)}2; Dipp 2,6-i-Pr2C6H3] provides the Mg(I) species, [{SiNDipp}MgNa]2, in which long Mg–Mg bond (>3.2 Å) is augmented by persistent Na–aryl interactions. Computational assessment indicates that this molecule best considered to comprise a contiguous tetrametallic core, viewpoint borne out its reaction with CO, results ethynediolate formation mediated dissimilar metal centers.

Reduction of the indate complex In(NONAr )(μ-Cl)2 Li(OEt2 )2 (NONAr =[O(SiMe2 NAr)2 ]2- ; Ar=2,6-iPr2 C6 H3 ) with sodium generates InII diindane species [In(NONAr )]2 . Further reduction a mixture potassium and [2.2.2]crypt affords InI N-heterocyclic indyl anion )]- , which crystallizes non-contacted [K([2.2.2]crypt)]+ cation. The can also be isolated as indyllithium compound )(Li{THF}3 ), contains an In-Li bond. Density functional theory calculations show that HOMO is metal-centred lone...

Reaction of bismuth(II) compounds with sulfur gives mixtures [Bi(NONR)]2(μ2-Sn) (NONR = [O(SiMe2NR)2]2-). Examples for n 1 and 3 have been crystallographically verified R 2,6-iPr2C6H3 (Dipp) tBu, the pentasulfide (n 5) Dipp. The corresponding product from reaction new Bi(II) radical Bi(NONAr‡)• (Ar‡ C6H2(CHPh2)2-tBu-2,6,4) exists as dimer [Bi(NONAr‡)(S4)]2, π*(SOMO)-π*(SOMO) interactions linking chains through trans-antarafacial pancake bonds.

The seven-membered cyclic potassium alumanyl species, [{SiNMes }AlK]2 }={CH2 SiMe2 N(Mes)}2 ; Mes=2,4,6-Me3 C6 H2 ], which adopts a dimeric structure supported by flanking K-aryl interactions, has been isolated either direct reduction of the iodide precursor, }AlI], or in stepwise manner via intermediate dialumane, }Al]2 . Although dialumane not observed Dipp-substituted analogue (Dipp=2,6-i-Pr2 H3 ), partial oxidation [{SiNDipp , where {SiNDipp N(Dipp)}2 provided extremely encumbered reacts...

Like the previously reported potassium-based system, rubidium and cesium reduction of [{SiNDipp}AlI] ({SiNDipp} = {CH2SiMe2NDipp}2) with heavier alkali metals [M Rb Cs] provides dimeric group 1 alumanyl derivatives, [{SiNDipp}AlM]2. In contrast, similar treatment sodium results in over-reduction incorporation a formal equivalent [{SiNDipp}Na2] into resultant species. The K, Rb, Cs compounds display variable efficacy toward C-H oxidative addition arene bonds at elevated temperatures (Cs > 110...

The potassium alumanyl [{SiNDipp}AlK]2 (SiNDipp = {CH2SiMe2NDipp}2; Dipp 2,6-i-Pr2C6H3) reacts with organic azides via reductive N2 elimination. With the less sterically encumbered PhN3 and C10H15N3 (1-azidoadamantane), putative initially formed aluminium imide undergoes facile [2 + 3] cycloaddition to provide tetrazenylaluminates [{SiNDipp}Al-κ2-N,N′-({N(R)}2N2)]K (R Ph, C10H15). In contrast, each Al(I) centre of only a single equivalent 2,4,6-Me3C6H2N3 imidoaluminate...

Abstract Bismuth diphenylphosphanides Bi(NON R )(PPh 2 ) (NON =[O(SiMe NR) ], R= t Bu, 2,6‐ i Pr C 6 H 3 , Aryl) undergo facile decomposition via single‐electron processes to form reduced Bi and P species. The corresponding derivatives )(PCy are stable. Reaction of the isolated II radical . Ar with white phosphorus (P 4 proceeds reversible selective activation a single P−P bond afford bimetallic μ,η 1:1 ‐bicyclo[1.1.0]tetraphosphabutane compound.

The synthesis and catalytic properties of a series magnesium compounds consisting monoanionic, N,N'-chelating ligands (N∩N = amidinates, guanidinates, phosphaguanidinates) is reported. were synthesized by (i) insertion carbodiimide into an existing Mg–C or Mg–N bond, (ii) protonolysis organomagnesium compound neutral pre-ligand. Structural analyses mono- bis-(chelate) with general formula Mg(N∩N)X(L)n Mg(N∩N)2(L)n (X halide, aryloxide, amide; L Et2O, THF; n 0, 1 2) have been performed the...

Abstract More than 80 years after Paneth’s report of dimethyl bismuth, the first monomeric Bi II radical that is stable in solid state has been isolated and characterized. Reduction diamidobismuth(III) chloride Bi(NON Ar )Cl (NON =[O(SiMe 2 NAr) ] 2− ; Ar=2,6‐ i Pr C 6 H 3 ) with magnesium affords . ). X‐ray crystallographic measurements are consistent a two‐coordinate bismuth +2 oxidation no short intermolecular contacts, solid‐state SQUID magnetic indicate paramagnetic compound single...

Chloride abstraction from the diamido-bismuth compound Bi(Me2Si{NAr}2)Cl (1, Ar = 2,6-i-Pr2C6H3) using MCl3 (M Al, Ga) is a facile route to cationic species. Stoichiometric reactions afford tetrachlorometallate salts [Bi(Me2Si{NAr}2)][MCl4] (2a, M Al; 3a, Ga), whereas reaction with 0.5 equiv of group 13 reagent gives μ-chlorido bridged cations [{Bi(Me2Si{NAr}2)}2(μ-Cl)][MCl4] (2b, 3b, Ga). The crystal structure 2a shows formally two-coordinate bismuth cation, Bi···Cl contact [AlCl4]− anion,...

Mg(mesC{NCy}2)(N{SiMe3}2)(THF) is a (pre)catalyst for C–C bond formation. Attempted isolation of intermediates in proposed catalytic cycle was hindered by facile ligand redistribution. A subsequent investigation commercially available organo- or amidomagnesium(II) compounds (including Grignard reagents) demonstrated similar behavior.

Pyridine substituted with one and two bicyclic guanidine groups has been studied as a potential source of superbases. 2-{hpp}C5H4N (I) 2,6-{hpp}2C5H3N (II) (hppH = 1,3,4,6,7,8-hexahydro-2H-pyrimido[1,2-a]pyrimidine) were protonated using [HNEt3][BPh4] to afford [I-H][BPh4] (1a), [II-H][BPh4] (2), [II-H2][BPh4]2 (3). Solution-state 1H 15N NMR spectroscopy shows symmetrical cation in 2, indicating facile proton-exchange process solution. Solid-state data differentiates between the groups,...

Bis(amidodimethyl)disiloxane ligands derived from O{SiMe2N(H)R}2 (abbreviated as (NONR)H2) are a stable support for neutral and cationic bismuth compounds. Attempts to extend the series Bi(NONR)Cl (R = Ar 2,6-iPr2C6H3; R tBu) include compounds where Ar' 2,6-Me2C6H3 were complicated by concomitant formation of bimetallic compound {Bi(NONAr')}2(μ-NONAr'). Compounds containing [Bi(NONR)]+ cations obtained reactions with group 13 chlorides MCl3 (M Al, Ga). X-ray crystallographic analysis showed...

The bis(amidodimethyl)disiloxane antimony chlorides Sb(NONR )Cl (NONR =[O(SiMe2 NR)2 ]2- ; R=tBu, Ph, 2,6-Me2 C6 H3 =Dmp, 2,6-iPr2 =Dipp, 2,6-(CHPh2 )2 -4-tBuC6 H2 =tBu-Bhp) are reduced to SbII and SbI species by using MgI reagents, [Mg(BDIR' )]2 (BDI=[HC{C(Me)NR'}2 ]- R'=2,4,6-Me3 =Mes, Dipp). Stoichiometric reactions with (R=tBu, Ph) form dimeric stibanes [Sb(NONR , shown crystallographically contain Sb-Sb single bonds. analogous distibane R=Dmp substituents has an exceptionally long...

Hydrocarbon-soluble β-diketiminato phenylcalcium derivatives, which display various modes of Ca-μ

Abstract The dimeric β‐diketiminato calcium hydride, [( Dipp BDI)CaH] 2 ( BDI = HC{(Me)CN‐2,6‐ i ‐Pr C 6 H 3 } ), reacts with ortho ‐, meta ‐ or para ‐tolyl mercuric compounds to afford hydridoarylcalcium compounds, BDI) Ca (μ‐H)(μ‐ o m p ‐tolyl)], in which dimer propagation occurs either via μ ‐η 1 bridging between the centers. In each case, orientation and hapticity of aryl units is dependent upon position methyl substituent. While wholly organometallic dimers, BDI)Ca( ‐tolyl)] , can be...

Abstract Reactions of the potassium alumanyl derivative, [K{Al(SiN Dipp )}] 2 (SiN ={CH SiMe NDipp} ), with white phosphorus result in two electron reduction to provide controlled access species containing (P 4 ) 2− dianion. Two examples have been crystallographically characterized, a monomeric derivative which cation is encapsulated by 18‐crown‐6 (18‐cr‐6) and 1‐dimensional polymeric isolated from diethyl ether solution. Although reactions performed at more elevated temperatures presence...