peri-Substituted naphthalene derivatives 1-BCy 2 -8-SnL-C 10 H 6 (5), 1-PPh 2 -8-SnL-C 10 H 6 (6), and 1,8-(SnL) 2 -C 10 H 6 (7) (L = 2,6-(Me 2 NCH 2 ) 2 C 6 H 3 ) were prepared. Compounds 5−7 allowed us to study the interactions between the tin atom from the LSn fragment with either Lewis acidic (BCy 2 ) or Lewis basic sites (PPh 2 and LSn). Moreover, addition of an external Lewis acid (BH 3• SMe 2 ) to 6 with different Sn/P donor atoms surprisingly provided the complex 1-PPh 2 -8-[(BH 3 ) 2 L]Sn-C 10 H 6 (8), where both CH 2 NMe 2 groups of the ligand L were coordinated by BH 3 and as the consequence, P → Sn coordination exists in 8. The presence and type of the Y/Sn (P → Sn vs B ← Sn) interactions are described either experimentally or theoretically. The latter comprise determination of peri-interaction energies (PIE) as well as a variety of real-space bonding indicators (RSBI) derived from DFT calculations on the C/B−H corrected XRD structures of compounds 5−8. The electron density (ED) is topologically dissected according to the Atoms-In-Molecules (AIM) approach providing atomic volumes and charges as well as a bond paths motif, which also includes weak secondary contacts thereby transcending the Lewis picture of molecular bonding patterns.

The aim of this review is to summarize recent achievements in the field of (N),C,N‐coordinated group 13–15 compounds not only regarding their synthesis and structure, but mainly focusing on their potential applications. Relevant compounds contain various types of N‐coordinating ligands built up on an ortho‐(di)substituted phenyl platform. Thus, group 13 and 14 derivatives were used as single‐source precursors for the deposition of semiconducting thin films, as building blocks for the preparation of high‐molecular polymers with remarkable optical and chemical properties or as compounds with interesting reactivity in hydrometallation processes. Group 15 derivatives function as catalysts in the Mannich reaction, in the allylation of aldehydes or activation of CO2. They were used as transmetallation reagents in transition metal catalysed coupling reactions. The univalent species serve as ligands for transition metals, activate alkynes or alkenes and are utilized as catalysts in the transfer hydrogenation of azo‐compounds.

A stable ionic κ2Sn,P-coordinated Ru complex was used as an efficient catalyst for aerobic oxidation reactions.

Set of [Ru(η6‐cymene)(R)XCl] (R=L1SnCl, L1GeCl L2PPh2, X=Cl or SnCl3, L1=[2‐(CH2NEt2)‐4,6‐(tBu)2C6H2]−, L2=2,6‐iPr2‐C6H3‐NH−) catalysts was tested in aerobic oxidations of primary amines. The activity of studied catalysts depends on the charge of the Ru atom that has been influenced either by donating ligands R or by character of X. Typical Ru/P catalyst [Ru(η6‐cymene)(L2PPh2)Cl2] (3) with least negative charge on the Ru atom has been observed as the most effective. The design of the phosphine ligand L2 containing amino‐phosphine PNH moiety provided efficient anchoring of complex 3 to silica gel via hydrogen bonding of the PNH functional group to SiO2 to give heterogeneous catalyst 3‐silica. This complex has been also efficiently tested in aerobic oxidation as recyclable catalyst with cumulative TON up to 6930.

Peri‐substituted naphthalene derivatives, namely, N‐coordinated plumbylenes 1‐PPh2‐8‐PbL‐C10H6 (4) and 1‐BCy2‐8‐PbL‐C10H6 (5) (L = 2,6‐(Me2NCH2)2C6H3) were prepared. Compounds 4 and 5 allowed studying interactions between the Pb atoms with the either Lewis acidic (BCy2) or Lewis basic sites (PPh2). Addition of an external Lewis acid (BH3·SMe2) to 5 provided the complex 1‐BCy2‐8‐[(BH3)2L]Pb‐C10H6 (7), in which both NMe2 groups of the ligand L were coordinated by BH3. This reaction has also been used for the synthesis of a tin analogue 1‐BCy2‐8‐[(BH3)2L]Sn‐C10H6 (6). New complexes 4–7 were also compared with the previously known, tin(II) analogues 1‐PPh2‐8‐SnL‐C10H6 (1), 1‐PPh2‐8‐[(BH3)2L]Sn‐C10H6 (2), 1‐BCy2‐8‐SnL‐C10H6 (3). This set of compounds allowed us to study influence of the P→E and E→B peri‐contacts upon the redox potentials E1/2 (ox1) by the cyclic voltammetry. As the result, the selective oxidation of E(II) atom was also studied and the new organotin(IV) sulfide [1‐PPh2‐8‐LSn(C10H6)(µ‐S)]2 (9) was prepared, the product of exclusive oxidation of the tin(II) atom in 1. Beside this, the evaluation of the P→E and E→B peri‐contacts in the neutral molecules, the first and second ionization energies (IE) were calculated. For this reason, electronic properties, full structural optimizations were conducted with density functional theory (DFT) for all possible combinations of metal atom (Sn vs. Pb), Lewis acid (N→Sn/Pb vs. N(BH3)Sn/Pb), peri‐substituents (BCy2 vs. PPh2), and for three molecular charges (0 vs. 1+ vs. 2+) on the B3PW91/6‐311+g(2df,p) level of theory.