Reactivity of Chalcogenostannate Salts: Unusual Synthesis and Structure of a Compound Containing Ternary Cluster Anions [Co4(μ4-Se)(SnSe4)4]10

Abstract

Dedicated to Professor Dieter Fenske on the occasion of his 60th birthdayThe stabilization of binary aggregates of main group elements [E 0x E y ] qÀ in the coordination sphere of transitionmetal ions M nþ (E' or E ¼ Group 13±15 or 16 element), and thus the formation of structures that contain ternary heavy atom frameworks, is an area of increasing research activity. [1±16] Besides diverse range of molecular and crystal structures, the synthesis of some ternary M/E'/E systems that show polymeric anion substructures representing ™open solidstate structures∫, as found in Rb 3 [AgGe 4 Se 10 ]¥2 H 2 O [10] or K 2 [MnSnS 4 ], [11] have recently attracted attention. Such compounds combine both zeolite-type and semiconducting properties. If binary alloys or salts of binary anions are used for the construction of the E'/E aggregates instead of separate components, the investigations additionally serve to study the reaction behavior and stability of these systems in the presence of transition-metal compounds. However, most reports on the latter deal with binary reactants of Groups 15/16, [1, 13±16] for example the synthesis of [PPh 4 ] 2 -[Mn(CO) 3 (As 3 Se 3 ) 5 ] by using [As 4 Se 4 ]. [13b] Only most recently, were some results published that considered the surfactanttemplated solvothermal synthesis of mesoporous solids like (C 16 H 33 NC 5 H 5 ) x [Pt y Sn 0 4 Se 10 ] (x ¼ 1.9±2.8; y ¼ 0.9±1.6).[12] One of our current aims is to generate coordination compounds by reacting binary anions of Groups 14 and 16.

Solvothermal syntheses of three new one-dimensional ternary selenidostannates: [DBNH][M1/2Sn1/2Se2] (M=Mn, Zn, Hg)

“…It is well known that group 13 (Ga, In) and 14 (Ge, Sn) metals normally combined with chalcogen elements (S, Se, Te) in tetrahedral geometry and formed M′Q 4 tetrahedra [26][27][28], which are the primary building units in setting up the structures of 1D chalcogenides. For group 13 metals, the M′Q 4 tetrahedra usually connect to each other via edge-sharing and generate a large number of [M′Q 2 ] n n− (M′¼Ga, In; Q¼ S, Se, Te) chains, which are templated by alkali metals, organic amines, and transition-metal complexes [29][30][31][32][33][34][35][36] [47][48][49][50].…”

Ortho‐Chalcogenostannates as Ligands: Syntheses, Crystal Structures, Electronic Properties, and Magnetism of Novel Compounds Containing Ternary Anionic Substructures [M4(μ4‐Se)(SnSe4)4]10− (M=Mn, Zn, Cd, Hg), ${{{\hfill 3\atop \hfill \infty }}}${[Hg4(μ4‐Se)(SnSe4)3]6−}, or ${{{\hfill 1\atop \hfill \infty }}}${[HgSnSe4]2−}

“…We are interested in synthesizing and characterizing systems with ternary structural units by the reaction of ortho‐selenostannate anions [SnSe 4 ] 4− , the behavior of which towards transition metal compounds is still largely unknown. In the course of our investigations,8, 9 we recently isolated and structurally characterized quaternary compounds [K 22 (MeOH) 17 (H 2 O) 8 ][Co 4 (μ 4 ‐Se)(SnSe 4 ) 4 ] ( 1 a ),9a [K 36 (μ 6 ‐Cl) 2 (H 2 O) 11 (MeOH) 32 ][SnSe 4 ][Co 4 (μ 4 ‐Se)(SnSe 4 ) 4 ] 3 ( 1 b )9 and [K 10 (H 2 O) 16 (MeOH) 0.5 ][M 4 (μ 4 ‐Se)(SnSe 4 ) 4 ] (M=Zn: 2 , M=Mn: 3 ),9c which contain the formerly unknown type of ternary selenide anion [M 4 (μ 4 ‐Se)(SnSe 4 ) 4 ] 10− . Compounds 1 – 3 were obtained by reactions of K 4 [SnSe 4 ]10 or K 4 [SnSe 4 ]⋅1.5 MeOH9c with [Co(en) 3 ]Cl 3 (en=1,2‐diaminoethane), MnCl 2 ⋅4 H 2 O, or ZnCl 2 in H 2 O/MeOH.…”

Solvothermal syntheses and structures of A3AgSn3Se8 (A=Rb, K)

“…Under relatively mild conditions, the molecular building blocks can be assembled to a fascinating variety of quaternary chacolgenides. However solvothermal synthesis has produced a limited number of quaternary chalcogenides up to now [10][11][12][13][14]. To some extent, this situation results from deficient research on mineralizers for the synthesis.…”