Formation and Reactivity of Organo‐Functionalized Tin Selenide Clusters

Abstract

Reactions of R(1) SnCl3 (R(1) =CMe2 CH2 C(O)Me) with (SiMe3 )2 Se yield a series of organo-functionalized tin selenide clusters, [(SnR(1) )2 SeCl4 ] (1), [(SnR(1) )2 Se2 Cl2 ] (2), [(SnR(1) )3 Se4 Cl] (3), and [(SnR(1) )4 Se6 ] (4), depending on the solvent and ratio of the reactants used. NMR experiments clearly suggest a stepwise formation of 1 through 4 by subsequent condensation steps with the concomitant release of Me3 SiCl. Furthermore, addition of hydrazines to the keto-functionalized clusters leads to the formation of hydrazone derivatives, [(Sn2 (μ-R(3) )(μ-Se)Cl4 ] (5, R(3) =[CMe2 CH2 CMe(NH)]2 ), [(SnR(2) )3 Se4 Cl] (6, R(2) =CMe2 CH2 C(NNH2 )Me), [(SnR(4) )3 Se4 ][SnCl3 ] (7, R(4) =CMe2 CH2 C(NNHPh)Me), [(SnR(2) )4 Se6 ] (8), and [(SnR(4) )4 Se6 ] (9). Upon treatment of 4 with [Cu(PPh3 )3 Cl] and excess (SiMe3 )2 Se, the cluster fragments to form [(R(1) Sn)2 Se2 (CuPPh3 )2 Se2 ] (10), the first discrete Sn/Se/Cu cluster compound reported in the literature. The derivatization reactions indicate fundamental differences between organotin sulfide and organotin selenide chemistry.

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

“…As reported previously, [12,18] Although residual electron density was observed at a reasonable distance from the Se atom on the difference Fourier map, refinement of the proton at the terminal Se atom in 1 was not successful. As reflected in a relatively large anisotropic displacement parameter of the Se atom, some disorder of this ligand seems to be present, hence inhibiting a better refinement of the SeH group.…”

“…[(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. 1 H and 31 P NMR spectra were recorded with a Bruker ARX 300 spectrometer.…”

“…[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. Its photoluminescence and absorption spectra are discussed as well.…”

Amino Acid Functionalized Organotin Trichlorides and Their Tin Sulfide Clusters

“…[4,5] Such clusters have been isolated in many different inorganic core architectures, with the most dominant ones possessing a defect-heterocubane-type [(RSn) 3 S 4 Cl], a "doppeldecker"-type [(RSn) 4 S 6 ], and the isomeric adamantane-type structure [(RSn) 4 S 6 ], respectively. [5][6][7][8][9][10][11][12][13] Metal chalcogenide clusters furthermore play an important role for bio-relevant developments. [14] Here, tin sulfide clusters can be potentially useful as cytotoxic agents, as they decompose under slightly acidic conditions to release cytotoxic H 2 S. [15] This may allow for a targeted delivery of H 2 S to undesirable cells, the environment of which can be more acidic than that of healthy cells.…”

“…[7] However, upon amino acid derivatives being added, this led to intramolecular condensation reactions between the keto functionalized substituent R 1 at one cluster Sn atom and a terminal amine group at the amino acid attached to R 1 at another cluster Sn atom. [7] However, upon amino acid derivatives being added, this led to intramolecular condensation reactions between the keto functionalized substituent R 1 at one cluster Sn atom and a terminal amine group at the amino acid attached to R 1 at another cluster Sn atom.…”