Functionalized Organotin‐Chalcogenide Complexes That Exhibit Defect Heterocubane Scaffolds: Formation, Synthesis, and Characterization

Abstract

The synthesis of new functionalized organotin-chalcogenide complexes was achieved by systematic optimization of the reaction conditions. The structures of compounds [(R(1, 2) Sn)3 S4 Cl] (1, 2), [((R(2) Sn)2 SnS4 )2 (μ-S)2 ] (3), [(R(1, 2) Sn)3 Se4 ][SnCl3 ] (4, 5), and [Li(thf)n ][(R(3) Sn)(HR(3) Sn)2 Se4 Cl] (6), in which R(1) =CMe2 CH2 C(O)Me, R(2) =CMe2 CH2 C(NNH2 )Me, and R(3) =CH2 CH2 COO, are based on defect heterocubane scaffolds, as shown by X-ray diffraction, (119) Sn NMR spectroscopy, and ESI mass spectrometry analyses. Compounds 4, 5, and 6 constitute the first examples of defect heterocubane-type metal-chalcogenide complexes that are comprised of selenide ligands. Comprehensive DFT calculations prompted us to search for the formal intermediates [(R(1) SnCl2 )2 (μ-S)] (7) and [(R(1) SnCl)2 (μ-S)2 ] (8), which were isolated and helped to understand the stepwise formation of compounds 1-6.

Formation and Reactivity of Organo‐Functionalized Tin Selenide Clusters

“…The formation of the ionic compounds C or D from the neutral compounds 3 or 6 , and their subsequent co‐crystallization, can be attributed to a (partial) decomposition of the neutral species in solution with reductive formation of the [Sn II Cl 3 ] − counterion and oxidation of the ligand R 1 , as discussed previously …”

“…The first neutral DC tin sulfide cluster, [(SnR 1 ) 3 S 4 Cl] (R 1 =CMe 2 CH 2 C(O)Me), was obtained by reaction of R 1 SnCl 3 (A) with (SiMe 3 ) 2 S . Investigations of this system have shown that different cluster topologies can be selectively and systematically obtained by tuning the Sn/S ratio of the corresponding precursor mixture, thereby initiating a stepwise reaction cascade between R 1 SnCl 3 and S(SiMe 3 ) 2 with the concomitant release of Me 3 SiCl.…”

“…The first DC‐type tin selenide cluster with purely organic ligands to be published was [Na(MeOH) 2 ][R COO (R COO H) 2 Sn 3 Se 4 ][R COO 2 (R COO H)Sn 3 Se 4 ], obtained by in situ generation of Na 2 Se in liquid ammonia and subsequent addition of R COO HSnCl 3 . Recent work in our group has showcased the chemistry of Sn/Se as well as Sn/Te clusters starting from R 1 SnCl 3 ( A ) and (SiMe 3 ) 2 Se ( B ) or (SiMe 3 ) 2 Te as precursors in room‐temperature syntheses. The ionic compound [(SnR 1 ) 3 Se 4 ][SnCl 3 ] ( C ) was obtained upon redissolving the white precipitate that formed on treatment of A with B in toluene.…”

“…The ionic compound [(SnR 1 ) 3 Se 4 ][SnCl 3 ] ( C ) was obtained upon redissolving the white precipitate that formed on treatment of A with B in toluene. The corresponding hydrazone derivative [(SnR 2 ) 3 Se 4 ][SnCl 3 ] ( D ) resulted from the reaction of C with hydrazine hydrate (Scheme ) …”

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.…”