Five peri-substituted naphthalene and acenaphthalene complexes (Ph 2 Pn) 2 Naph (E = Sb 1, Bi 3), (Ph 2 Sb) 2 Acenaph (2), (Ph 2 Bi)(Me 3 Sn)Naph (4) and (PhBiNaph) 2 (5) were synthesized and characterized in solution ( 1 H, 13 C NMR, IR) and in the solidstate (sc-XRD). 1-5 show different types of noncovalent intermolecular interactions in the solid-state including NaphÀ H•••π, π•••π and Bi•••π (5) contacts, which were exemplarily (5) quantified by use of density functional theory and local coupled cluster electronic structure theory calculations, demonstrating that the Bi•••π contact provides the main stabilizing contribution. Symmetry-adapted intermolecular perturbation theory calculations showed that this and other contacts are dominated by London dispersion interactions.

Syntheses and solid-state structures of diarsane Naph2As2 (Naph = 1,8-naphthalenediyl, 1) and (Naph)5Sb4Cl2 3 are reported and the σ-donor capacity of Naph2E2 (E = As 1, Sb 2) was studied in reactions with (coe)Cr(CO)5 (coe = Z-cyclooctene), yielding Naph2As2[Cr(CO )5]2 (4) and Naph2E2Cr(CO)5 (E = As 5, Sb 6). In contrast, reactions of 1 and 3 with Me2SAuCl proceed with oxidation and formation of elemental gold as well as Naph2(AsCl)2 ( 7) and [NaphSbCl2]2 8. All complexes were characterized by elemental analyses, heteronuclear ( 1 H, 13 C) NMR and FT-IR spectroscopy as well as single crystal X-ray diffraction. Intermolecular E•••π interactions (E = As, Sb), which were observed in 7 and 8, were quantified by use of density functional theory and local coupled cluster electronic structure theory calculations. These allow to assess the nature and relative importance of covalent and non-covalent interactions and illustrate how dispersion interactions change with the electronic structure of the series of compounds.

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).

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.

We report the synthesis and solid-state structures of DMAP-coordinated ([L(DMAP)GaPn]2[OTf]2; Pn = Sb 3, Bi 4) and base-free dipnictene dications ([LGaPn]2[BArFx]2, Pn = Sb: x = 24, 5a; 20, 5b;...