The chalcogen bond is a nonclassical σ-hole-based noncovalent interaction with emerging applications in medicinal chemistry and material science. It is found in organic compounds, including 2D aromatics, but has so far never been observed in 3D aromatic inorganic boron hydrides. Thiaboranes, harboring a sulfur heteroatom in the icosahedral cage, are candidates for the formation of chalcogen bonds. The phenyl-substituted thiaborane, synthesized and crystalized in this study, forms sulfur⋅⋅⋅π type chalcogen bonds. Quantum chemical analysis revealed that these interactions are considerably stronger than both in their organic counterparts and in the known halogen bond. The reason is the existence of a highly positive σ-hole on the positively charged sulfur atom. This discovery expands the possibilities of applying substituted boron clusters in crystal engineering and drug design.

We report here the synthesis of new C,N-chelated chlorostannylenes and germylenes L(3) MCl (M=Sn(1), Ge (2)) and L(4) MCl (M=Sn(3), Ge (4)) containing sterically demanding C,N-chelating ligands L(3, 4) (L(3) =[2,4-di-tBu-6-(Et2 NCH2 )C6 H2 ](-) ; L(4) =[2,4-di-tBu-6-{(C6 H3 -2',6'-iPr2 )N=CH}C6 H2 ](-) ). Reductions of 1-4 yielded three-coordinate C,N-chelated distannynes and digermynes [L(3, 4) M]2 for the first time (5: L(3) , M=Sn, 6: L(3) , M=Ge, 7: L(4) , M=Sn, 8: L(4) , M=Ge). For comparison, the four-coordinate distannyne [L(5) Sn]2 (10) stabilized by N,C,N-chelate L(5) (L(5) =[2,6-{(C6 H3 -2',6'-Me2 )NCH}2 C6 H3 ](-) ) was prepared by the reduction of chlorostannylene L(5) SnCl (9). Hence, we highlight the role of donor-driven stabilization of tetrynes. Compounds 1-10 were characterized by means of elemental analysis, NMR spectroscopy, and in the case of 1, 2, 5-7, and 10, also by single-crystal X-ray diffraction analysis. The bonding situation in either three- or four-coordinate distannynes 5, 7, and 10 was evaluated by DFT calculations. DFT calculations were also used to compare the nature of the metal-metal bond in three-coordinate C,N-chelating distannyne [L(3) Sn]2 (5) and related digermyme [L(3) Ge]2 (6).

The reduction of N,C,N-chelated bismuth chlorides [C6H3-2,6-(CH=NR)2]BiCl2 [where R = tBu (1), 2',6'-Me2C6H3 (2), or 4'-Me2NC6H4 (3)] or N,C-chelated analogues [C6H2-2-(CH=N-2',6'-iPr2C6H3)-4,6-(tBu)2]BiCl2 (4) and [C6H2-2-(CH2NEt2)-4,6-(tBu)2]BiCl2 (5) is reported. Reduction of compounds 1-3 gave monomeric N,C,N-chelated bismuthinidenes [C6H3-2,6-(CH=NR)2]Bi [where R = tBu (6), 2',6'-Me2C6H3 (7) or 4'-Me2NC6H4 (8)]. Similarly, the reduction of 4 led to the isolation of the compound [C6H2-2-(CH=N-2',6'-iPr2C6H3)-4,6-(tBu)2]Bi (9) as an unprecedented two-coordinated bismuthinidene that has been structurally characterized. In contrast, the dibismuthene {[C6H2-2-(CH2NEt2)-4,6-(tBu)2]Bi}2 (10) was obtained by the reduction of 5. Compounds 6-10 were characterized by using (1)H and (13)C NMR spectroscopy and their structures, except for 7, were determined with the help of single-crystal X-ray diffraction analysis. It is clear that the structure of the reduced products (bismuthinidene versus dibismuthene) is ligand-dependent and particularly influenced by the strength of the N→Bi intramolecular interaction(s). Therefore, a theoretical survey describing the bonding situation in the studied compounds and related bismuth(I) systems is included. Importantly, we found that the C3NBi chelating ring in the two-coordinated bismuthinidene 9 exhibits significant aromatic character by delocalization of the bismuth lone pair.

The series of organotin(IV) complexes L 1-3 SnPh n Cl 3-n , where L 1-3 are O,C,O-chelating ligands (called the pincer ligands), 2,6-bis(alkoxymethyl)phenyl-, 2,6-, have been synthesized and characterized by 1 H, 13 C, and 119 Sn NMR spectroscopy, MS-ESI spectrometry, and elemental analysis. The structure of selected compounds L 1 SnPh 3 (1), L 1 SnPh 2 Cl (2), L 1 SnPhCl 2 (3), L 1 SnCl 3 (4), L 2 SnPhCl 2 (7), and L 3 SnPhCl 2 (11) was studied by X-ray crystallography and 119 Sn CP/ MAS NMR spectroscopy in the solid state. The determination of crystal structures reveals the similarity of all the shapes of coordination polyhedra. The deformations of the shapes of coordination polyhedra depend on the degree of donor-acceptor Sn-O interaction (from very weak (interatomic distance Sn-O 2.963(1) Å) to medium-strong (2.475(1) Å)), which increases with increasing Lewis acidity of the tin atom in the L 1-3 SnPh n Cl 3-n entities and decreases with increasing steric demands of substituents R (from Me to t-Bu). NMR spectroscopy indicates a similar structural arrangement of the studied compounds in solution.

A monatomic zerovalent silicon(0) complex (“silylone”) stabilized by the chelating bis­(silylenyl)-ortho-carborane ligand, 1,2-(LSi)2-1,2-C2B10H10 [L = PhC­(NtBu)2], has been synthesized from the redox reaction of the dipotassium bis­(silylenyl)-nido-carboranate salt, 1,2-(LSi)2-1,2-C2B10H10K2, and NHC-SiCl2 (NHC = {[HCN­(2,6-iPr2C6H3)]2C:}). Markedly different from previous examples, this silylone undergoes reduction due to the closo-C2B10 cluster backbone, which is prone to accept up to two electrons to form the cage-opened dianionic nido-C2B10 cluster core. Surprisingly, the closo-C2B10 core of the silylone consumes only one molar equiv of potassium naphthalenide, in addition, one electron is intramolecularly transferred from the Si0 atom to the C2B10 core to form an elusive bis­(silylene)-stabilized SiI radical cation which undergoes homocoupling to the corresponding isolable dicationic SiI–SiI complex.

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Dedicated to Professor Hansgeorg Schnöckel on the occasion of his 65th birthdayThe term "metalloid cluster" was coined by Schnöckel and coworkers in the context of Al chemistry to designate those metal clusters in which "the number of metal-metal contacts exceeds the number of metal-ligand contacts and by the presence of metal atoms which participate exclusively in metal-metal interactions".

119Sn, 15N, 13C, and 1H NMR spectra were studied for [2-(dimethylaminomethyl)phenyl]stannanes, R1R2R3R4Sn or R1R2R24Sn, where R1, R2, and R3 are 1-butyl, Cl or Br, the same or different, and R4 is 2-(dimethylaminomethyl)phenyl. The occurrence of intramolecular interaction between the nitrogen and tin atoms was demonstrated based on changes in the characteristic values of the NMR parameters of these nuclides (δ(15N), δ(119Sn), J(119Sn,15N), and their interrelations, as well as on the relatively high values of the coupling constants 3J(119Sn,13C(CH2)).