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Oxidative addition reactions of gallanediyl LGa and AsX3 yield gallaarsenes LGaAsGa(Cl)L (X = Cl 1; Br 2) with a Ga–As double bond.

We report the synthesis and structural characterization of Ga-substituted diarsene [L(OEt)GaAs]2, which is an exemplary case of a Ga-substituted dipnictene of the general type [L(X)Ga]2E2 (L=C[C(Me)N(2,6-i-Pr2-C6H3)]2, X = F, Cl, Br, I, NMe2, OEt, E = As, Sb, Bi). We examined this extended series of compounds computationally and found that attractive London dispersion interactions between the substituents on the N,N'-chelating β-diketiminate ligands as well as pnictogen-π interactions between the group 15 metal center and the ligand are a key factor for the stability and the electronic structures of such types of complexes.

The reactions of two equivalents of LGa {L = HC[C(Me)N(2,6-iPr 2 C 6 H 3 )] 2 } with SbX 3 (X = Br, I, OEt) proceed with elimination of LGaX 2 and formation of Ga-substituted distibenes

Room-temperature stable main group element carbonyl complexes are rare. Here we report on the synthesis of two such complexes, namely gallium-substituted silylene-carbonyl complexes [L(X)Ga]2SiCO (X = I 2, Me 3;...

The Front Cover illustrates the outcome of selected small molecule activation reactions using heteroleptic metallasilylenes L1(Cl)MSiL2, which are represented by the basic cards. By adding a “reACTION card”, displaying the small molecules CO2, N2O, or Me3SiN3, on top of a basic card, the corresponding “product cards”, which symbolize the resulting carbonate complexes, silanoic esters, and silaimine, have to be found and placed on the matching top card. This game can be enjoyed in a friendly atmosphere with a glass of wine. More information can be found in the Research Article by S. Schulz and co‐workers.

Small-molecule activation by low-valent main-group element compounds is of general interest. We here report the synthesis and characterization ( 1 H, 13 C, 29 Si NMR, IR, sc-XRD) of heteroleptic metallasilylenes L 1 (Cl)MSiL 2 (M = Al 1, Ga 2, L 1 = HC[C(Me)NDipp] 2 , Dipp = 2,6-i Pr 2 C 6 H 3 ; L 2 = PhC(N t Bu) 2 ). Their electronic nature was analyzed by quantum chemical compu-[a] J. Schoening, A.

Bond activation: An unprecedented [2+1+1] fragmentation of the P4 tetrahedron and formation of an eight‐membered M−P=Si−P=P−Si=P−M chain was achieved in reactions of white phosphorous with heteroleptic metallasilylenes. More information can be found in the Research Article by S. Schulz and co‐workers (DOI: 10.1002/chem.202201031).