Since the groundbreaking discovery in 2018 that synthesis of a bottleable nucleophilic aluminyl anion is feasible, handful derivatives have been developed to date, which are, however, limited diamino- and dialkyl-substituted species. Herein, we report cyclic (alkyl)(amino)aluminyl based on five-membered framework. The dicoordinate aluminum center features both lone pair electrons an unoccupied 3p orbital, thus genuinely making it isoelectronic with carbenes. We show bond formation activation...

Since aluminum is the most electropositive element among p-block elements, construction of molecules bearing a dianionic Al-Al σ-bond inherently highly challenging. Herein, we report first synthesis dialane(6) 2 based on Al2O three-membered ring scaffold, namely, an analog oxirane. The structure has been unambiguously ascertained by spectroscopic analysis as well X-ray crystallography, and computational studies revealed that bears strained σ-bond. readily reacts with unsaturated substrates...

The stable cyclic (alkyl)(amino)alumanyl anion (CAAAl) 3 reacts with white phosphorus (P4) under ambient conditions, in which P4 is fragmented into a P1 unit to afford the bis(alumanyl)phosphide 2, demonstrating direct formation of P from an Al anion. Structural and electronic features latter were fully characterized by standard spectroscopic means, X-ray diffraction analysis, computational studies, revealed that 2 bears highly polarized (δ+) (δ−) relatively short Al–P bonds, indicative...

A 1,3-diphosphacyclobutane-2,4-diyl contains a unique unsaturated cyclic unit, and the presence of radical-type centers have been expected as source functionality. This study demonstrates that P-heterocyclic singlet biradical captures muonium (Mu=[μ+ e- ]), light isotope hydrogen radical, to generate an observable paramagnetic species. Investigation powder sample 2,4-bis(2,4,6-tri-t-butylphenyl)-1-t-butyl-3-benzyl-1,3-diphosphacyclobutane-2,4-diyl using muon (avoided) level-crossing...

Abstract 9‐Phosphaanthracene (dibenzo[ b , e ]phosphorin, acridophosphine) has attracted interest as one of the heavier acenes. Herein, we demonstrate an efficient synthetic process that provides air‐tolerant 1,8‐bis(trifluoromethyl)‐9‐phosphaanthracenes. The sterically encumbered and electron‐withdrawing trifluoromethyl (CF 3 ) groups are quite advantageous not only to stabilize intrinsically unstable unsaturated phosphorus atom but also facilitate construction phosphinine skeleton based on...

The sterically encumbered 1‐amino‐1,3‐diphosphacyclobuten‐4‐yl anion, prepared from 1‐(2,4,6‐tri‐ tert ‐butylphenyl)‐2‐phosphaethyne and lithium diisopropylamide (0.5 equiv.), was characterized spectroscopically afforded air‐tolerant amino‐substituted 1,3‐diphosphacyclobutane‐2,4‐diyls by S N 2‐type alkylation arylation reactions with benzyne. photoabsorption electrochemical parameters of the P‐heterocyclic singlet open‐shell compounds revealed that they had higher electron‐donating...

In this communication, we report muon spin rotation/resonance (μSR) studies for understanding radical reactivity of 10-mesityl-1,8-bis(trifluoromethyl)-9-phosphaanthracene. Transverse-field rotation (TF-μSR) and avoided level-crossing resonance (μLCR) measurements successfully visualized a paramagnetic species produced by regioselective addition muonium (Mu) to the skeletal phosphorus atom. Density functional theory (DFT) calculations P-muoniation product suggested two possible isomers....

The reaction of 1,4,2,5-diazadiborinine (1) with two equivalents an aryl isonitrile afforded a bicyclic product containing indole unit (2) or ketenimine moiety (3), suggesting the generation B,N-carbene intermediate formed via [4+2] cycloaddition in initial step. employment tolyl(phenyl isonitrile)gold complex (PhNCAuTol) as substrate allowed (amino)(borata)carbene gold complexes (4, 5) to be accessed.

Abstract A 1,3‐diphosphacyclobutane‐2,4‐diyl contains a unique unsaturated cyclic unit, and the presence of radical‐type centers have been expected as source functionality. This study demonstrates that P‐heterocyclic singlet biradical captures muonium (Mu=[μ + e − ]), light isotope hydrogen radical, to generate an observable paramagnetic species. Investigation powder sample 2,4‐bis(2,4,6‐tri‐ t ‐butylphenyl)‐1‐ ‐butyl‐3‐benzyl‐1,3‐diphosphacyclobutane‐2,4‐diyl using muon (avoided)...

Abstract In this communication, we report muon spin rotation/resonance (μSR) studies for understanding radical reactivity of 10‐mesityl‐1,8‐bis(trifluoromethyl)‐9‐phosphaanthracene. Transverse‐field rotation (TF‐μSR) and avoided level‐crossing resonance (μLCR) measurements successfully visualized a paramagnetic species produced by regioselective addition muonium (Mu) to the skeletal phosphorus atom. Density functional theory (DFT) calculations P‐muoniation product suggested two possible...