Electrophilic AlIII species have long dominated the aluminum reactivity towards arenes. Recently, nucleophilic low‐valent AlI aluminyl anions have showcased oxidative additions towards arenes C−C and/or C−H bonds. Herein, we communicate compelling evidence of an AlII radical addition reaction to the benzene ring. The electron reduction of a ligand stabilized precursor with KC8 in benzene furnishes a double addition to the benzene ring instead of a C−H bond activation, producing the corresponding cyclohexa‐1,3(orl,4)‐dienes as Birch‐type reduction product. X‐ray crystallographic analysis, EPR spectroscopy, and DFT results suggest this reactivity proceeds through a stable AlII radical intermediate, whose stability is a consequence of a rigid scaffold in combination with strong steric protection.

Herein, the first stable anions K[SIPr Bp ] (4 a-K) and K[IPr Bp ] (4 b-K) (SIPr Bp = BpC{N(Dipp)CH 2 } 2 , IPr Bp = BpC{N(Dipp)CH} 2 ; Bp = 4-PhC 6 H 4 ; Dipp = 2,6-iPr 2 C 6 H 3 ) derived from classical N-heterocyclic carbenes (NHCs) (i.e. SIPr and IPr) have been isolated as violet crystalline solids. 4 a-K and 4 b-K are prepared by KC 8 reduction of the neutral radicals [SIPr Bp ] (3 a) and [IPr Bp ] (3 b), respectively. The radicals 3 a and 3 b as well as [Me-IPr Bp ] 3 c (Me-IPr Bp = BpC{N(Dipp)CMe} 2 ) are accessible as crystalline solids on treatment of the respective 1,3-imidazoli(ni)um bromides (SIPr Bp )Br (2 a), (IPr Bp )Br (2 b), and (MeÀ IPr Bp )Br (2 c) with KC 8 . The cyclic voltammograms of 2 a-2 c exhibit two oneelectron reversible redox processes in À 0.5 to À 2.5 V region that correspond to the radicals 3 a-3 c and the anions (4 a-4 c) À . Computational calculations suggest a closed-shell singlet ground state for (4 a-4 c) À with the singlet-triplet energy gap of 17-24 kcal mol À 1 .

Metallocenes are well-established compounds in organometallic chemistry, which can exhibit either coplanar or bent structures according to the nature of the metal center (M) and the cyclopentadienyl ligands (Cp). Herein,...

Phosphanylgallane with hydrogen and halogen substituents (RXGa−PHR, R=organic substituent, X=halogen/hydrogen) are regarded as putative suitable precursors for accessing Ga=P doubly bonded species. Herein, we report on the synthesis, structure, and bonding analysis of a series of Lewis base‐ and Lewis acid/base‐stabilized phosphanylgallane bearing P−H and Ga−Cl/H substitution. To avoid oligomerization, the treatment of IDip.GaCl3 and (IDip)GaH2Cl (IDip=1,3‐bis(2,6‐diisopropylphenyl) imidazole‐2‐ylidene) with LiPHR or LiPHR(BH3) (R=Ph, Tip, Mes, NiPr2, NCy2) affords the corresponding Lewis base and Lewis acid/base coordinated H,Cl‐functionalized monomeric phosphanylgallane, respectively. The structure of these derivatives were determined by spectroscopic and X‐ray crystallographic analyses. The observed Ga−P bond lengths are comparable to those previously reported phosphanylgallane analogues. The nature of the CIDip‐Ga coordination bond was assessed with Energy Decomposition Analysis, suggesting a relatively stable adduct. Reactions of the phosphanylgallane with Brønsted bases were investigated.

Electrophilic AlIII species have long dominated the aluminum reactivity towards arenes. Recently, nucleophilic low‐valent AlI aluminyl anions have showcased oxidative additions towards arenes C−C and/or C−H bonds. Herein, we communicate compelling evidence of an AlII radical addition reaction to the benzene ring. The electron reduction of a ligand stabilized precursor with KC8 in benzene furnishes a double addition to the benzene ring instead of a C−H bond activation, producing the corresponding cyclohexa‐1,3(orl,4)‐dienes as Birch‐type reduction product. X‐ray crystallographic analysis, EPR spectroscopy, and DFT results suggest this reactivity proceeds through a stable AlII radical intermediate, whose stability is a consequence of a rigid scaffold in combination with strong steric protection.

Stable anions ……based on classical N-heterocyclic carbenes (NHCs) can be prepared by KC 8 -reduction of the corresponding NHC radicals as reported by Diego M. Andrada, Rajendra S. Ghadwal et al. in their Research Article (e202215244). Thekey to the stability of these anions is the delocalization of the electron lone pair over the C2-biphenyl substituent. In the solid state,the anions form ahexameric tubular structure with biphenyl substituents pointing inwards,a saresult of intriguing cation-p interactions.T he spider weaves its web.

Stable anions …on classical N-heterocyclic carbenes can be prepared by KC 8 reduction of the corresponding NHC radicals as reported by Diego M. Andrada, Rajendra S. Ghadwal, and co-workers in their Research Article (e202215244). Thek ey to the stability of these anions is the delocalization of the electron lone pair over the C2biphenyl substituent. In the solid state,t he anions form ah exameric tubular structure with biphenyl substituents pointing inwards,a saresult of intriguing cation-p interactions.T he spider weaves its web.

Die ersten stabilen Anionen K[SIPr Bp ] (4 a-K) und K[IPr Bp ] (4 b-K) (SIPr Bp = BpC{N(Dipp)CH 2 } 2 , IPr Bp = BpC{N(Dipp)CH} 2 ; Bp = 4-PhC 6 H 4 ; Dipp = 2,6-iPr 2 C 6 H 3 ), die von klassischen N-heterocyclischen Carbenen (NHCs) abgeleitet sind (d. h. SIPr und IPr), wurden als violette kristalline Feststoffe isoliert. 4 a-K und 4 b-K wurden durch die Reduktion der neutralen Radikale [SIPr Bp ] (3 a) bzw. [IPr Bp ] (3 b) mit KC 8 hergestellt. Die Radikale 3 a und 3 b sowie [Me-IPr Bp ] (3 c) (MeÀ IPr Bp = BpC{N(Dipp)CMe} 2 ) liegen als kristalline Feststoffe vor, wenn die entsprechenden 1,3-Imidazoli(ni)umbromide (SIPr Bp )Br (2 a), (IPr Bp )Br (2 b) und (Me-IPr Bp )Br (2 c) mit KC 8 umgesetzt werden. Die Cyclovoltammogramme von 2 a-2 c zeigen zwei reversible Ein-Elektronen-Redoxprozesse im Bereich von À 0.5 bis À 2.5 V, die den Radikalen 3 a-3 c und den Anionen (4 a-4 c) À entsprechen. Quantenchemische Berechnungen deuten auf einen geschlossenschaligen Singulett-Grundzustand für (4 a-4 c) À mit einer Singulett-Triplett-Energielücke von 17-24 kcal mol À 1 hin.