In situ Ge–Ge bond formation under ambient conditions: synthesis, characterization and reactivity of organo-functionalized telluridogermanate complexes

Abstract

Unprecedented noradamantane-type compounds [(R(2,3)Ge)(4)Te(5)] (R(2) = CH(2)CH(2)COOH, R(3) = CH(CH(2)COOH)(2)), containing a Ge-Ge bond, yield from reactions of R(2,3)GeCl(3) with Na(2)Te or Li(2)Te in THF, while reactions with R(1)GeCl(3) (R(1) = CMe(2)CH(2)COMe) afford a double-decker-type cage [(R(3)Ge)(4)Te(6)]; by reaction with hydrazine, the latter reacts to the hydrazone functionalized, monomeric anion [(R(4)Ge)Te(2)](-) (R(4) = CMe(2)CH(2)CNNH(2)Me).

Formation and Reactivity of Organo‐Functionalized Tin Selenide Clusters

“…The compounds with DD topology ( 4 , 8 , and 9 ) show slight structural differences regarding their inorganic [Sn 4 Se 6 ] cores compared with each other and the homologous sulfur compounds [(SnR 1 ) 4 S 6 ] ( E , equivalent to 4 ) and [(SnR 2 ) 4 S 6 ] ( F , equivalent to 8 , for details see the Supporting Information) . Selected structural parameters of these related compounds are given in Table S1 (in the Supporting Information).…”

“…We assume that steric interactions between neighboring substituents inhibitt he closer approach of the hydrazine groups to the Sn/S core. As another consequence of their [16,17] Selected structural parameters of these related compounds are given in Ta ble S1 (in the SupportingI nformation).…”

“…The utilization of organic ligands that additionally comprise Lewis basic sites, such as carbonyl or carboxylate functionalities, enabled the stabilization of discrete clusters with DC topology through additional intramolecular O→Sn coordination, shown first for the anionic cluster Na 2 [(SnR COO ) 3 S 4 ] (R COOH =C 2 H 4 COO) . However, such ligands are also suitable for the stabilization of an isomeric tin sesquisulfide [Sn 4 S 6 ] architecture, namely the so‐called “double‐decker” (DD) topology . Different from the AD structure, two parallel four‐membered [(RSn) 2 (μ‐S) 2 ] rings are connected here by two Sn–(μ‐S)–Sn bridges.…”

“…[16] However,s uch ligands are also suitable for the stabilization of an isomeric tin sesquisulfide [Sn 4 S 6 ]a rchitecture, namely the so-called "double-decker" (DD) topology. [17] Different from the AD structure, two parallel four-membered [(RSn) 2 (m-S) 2 ]r ings are connected here by two Sn-(m-S)-Sn bridges. As confirmed by DFT calculations, the DD topology is favored over the isomeric AD scaffold as soon as intramolecular O!Sn coordination is possible.…”

Trigonal Bipyramidal Metalselenide Clusters with Palladium and Tin Atoms in Various Positions

“…However, as this generally allows for further extension of the cluster surface and attachment to solid substrates, one of our current aims is the synthesis and thorough investigation of metal chalcogenide clusters that comprise ligands with functional groups. [3][4][5][6][7][8] For accessing ternary, organo-functionalized chalcogenide clusters, in which main group (semi-)metal atoms are combined with transition metal atoms for an even finer tunable electronic situation, the use of organotetrel chalcogenide clusters like [(R 1 T) 3 E 4 Cl] or [(R 1 T) 4 E 6 ] [R 1 = CMe 2 CH 2 C(O)Me, T = Ge, Sn; E = S, Se, Te] has proven an efficient and versatile way. [5,[9][10][11][12][13][14] 3 is the first compound based on a [Pd 2 SnSe 2 ] moiety, which furthermore exhibits a functional organic group at the tin atom.…”