(N),C,N‐Coordinated Heavier Group 13–15 Compounds: Synthesis, Structure and Applications

Abstract

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.

Organopnictogen(iii) bis(arylthiolates) containing NCN-aryl pincer ligands: from synthesis and characterization to reactivity

“…11–15 Over time, aryl ligands with nitrogen pincer arms have afforded remarkable antimony and bismuth synthons for further unusual reactivity studies. 16,17 In this regard, our work revealed that NCN-pincer ligands, e.g. 2,6-(Me 2 NCH 2 ) 2 C 6 H 3 and 2,6-{MeN(CH 2 CH 2 ) 2 NCH 2 } 2 C 6 H 3 with sp 3 nitrogen as donor atoms, can provide a satisfactory ligand environment for the synthesis of low oxidation state organobismuth species, 18 arylpnictogen( iii ) carbonates, 19,20 the first peroxo R 1 2 Bi–O–O–BiR 1 2 [R 1 = 2,6-(Me 2 NCH 2 ) 2 C 6 H 3 ] derivative, 18 and hypercoordinated monoorganopnictogen( iii ) oxides.…”

Four‐Coordinate Germylene and Stannylene and their Reactivity towards Se & Te**

“…[2e,8,9] Due to their potential application and unprecedented bonding nature, there is always a quest to synthesize the new chalcogenides (Chart 1). [3,[6][7][8][9] The synthesis of these heavy ketones is very much dependent upon the bulkiness of the substituents as an increase in bulk favors the stabilization of double-bonded compounds (Ge/ Sn = X, X = S, Se, Te), while the decrease in the bulk furnishes cyclic E 2 X 2 moiety (E = Ge, Sn; X = S, Se, Te). [10,11] In order to synthesize the double-bonded chalcogenides, we utilized a bulky ligand 1 ((E)-1-(2-bromophenyl)-N-(2,6-dibenzhydryl-4methylphenyl)ethan-1-imine) with a sterically crowded Ar* group [Ar* = 2,6-(dibenzhydryl-4-methylphenyl] on the nitrogen atom.…”

“…[10,11] In order to synthesize the double-bonded chalcogenides, we utilized a bulky ligand 1 ((E)-1-(2-bromophenyl)-N-(2,6-dibenzhydryl-4methylphenyl)ethan-1-imine) with a sterically crowded Ar* group [Ar* = 2,6-(dibenzhydryl-4-methylphenyl] on the nitrogen atom. [12] Herein, we report sterically demanding chlorogermylene (2), chlorostannylene (3), homoleptic germylene (4), homoleptic stannylene (5), germaselenone (7), stannaselenone (8), and stannatellurone (9). All the compounds were studied by the multinuclear NMR and mass spectrometry.…”

“…The germanium/tin chalcogenides have already shown their potential as semiconducting materials, which further broadens the scope of these heavy ketones in material chemistry [6,7] . The standard strategy of synthesizing such heavy ketones involves the design of a suitable bulky ligand, which can protect the reactive E=X bond (E=Ge, Sn; X=S, Se, Te) [2e,8,9] . Due to their potential application and unprecedented bonding nature, there is always a quest to synthesize the new chalcogenides (Chart 1) [3,6–9] …”

“…The standard strategy of synthesizing such heavy ketones involves the design of a suitable bulky ligand, which can protect the reactive E=X bond (E=Ge, Sn; X=S, Se, Te) [2e,8,9] . Due to their potential application and unprecedented bonding nature, there is always a quest to synthesize the new chalcogenides (Chart 1) [3,6–9] …”