Thiostannate Tin–Tin Bond Formation in Solution: In Situ Generation of the Mixed‐Valent, Functionalized Complex [{(RSn^IV)₂(μ‐S)₂}₃Sn^III₂S₆]

Abstract

In broad daylight: The double-decker thiostannate [(RSn(IV))(4)S(6)] (1, R = CMe(2)CH(2)COMe) condenses to form [{(RSn(IV))(2)(mu-S)(2)}(3)Sn(III)(2)S(6)] (2; see picture). This mixed-valent complex, which formally contains both Sn(III) and Sn(IV) atoms as confirmed by Mössbauer spectroscopy and DFT calculations, forms by a complicated, concerted mechanism. Additionally, 2 provides six carbonyl groups for further derivatization.

Controlling the Architecture of Discrete Organotin Sulfide Molecules by Optimization of the Intramolecular Spacer Length

“…Two [Sn 6 S 10 ] moieties are then bridged by four R 5 spacers, resulting in the discrete cavitand architecture with a cavity size of about 108 3 .…”

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

“…The structural motif of a [Pd 3 Se 2 ] 2+ bipyramid was described for one further cluster, [Pd 3 Se 2 (SeSiMe 3 ) 2 (PPh 3 ) 4 ], with very similar structural features, yet within a neutral molecule. [21] 3 is a neutral cluster, and it has an analogous topology, yet it unprecedentedly comprises two Pd atoms and one Sn atom within the trigonal bipyramidal cluster core.…”

“…All solvents were dried and freshly distilled prior to use. [(R 1 Sn) 4 Se 6 ], [(R 1 Sn) 3 Se 4 ]Cl, and (SiMe 3 ) 2 Se were prepared according to literature procedures. [12,29] Further chemicals were purchased from Sigma Aldrich.…”

“…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.…”

“…[17] Herein, we report on a recent study, in which previous reactions of organogermanium sulfide clusters with Pd complexes were transferred to organotin selenide clusters. For this, the precursors shown in Scheme 1, [(R 1 Sn) 3 …”