S. S. Yarovoi

Inorganic Coordination Polymers Based on Chalcocyanide Cluster Complexes

The paper reports results of experiments involving design of inorganic coordination polymers based on tetrahedral and octahedral chalcocyanide cluster complexes as building blocks. Various approaches to designing three‐dimensional, layered, and chain‐like structures are discussed. Structures of various types are described, and prospects of further studies in this field are outlined.

Synthesis of octahedral rhenium cluster chalcobromides Re6X4Br10 and Re6X8Br2 (X = S, Se, Te) by condensation from triangular rhenium bromide Re3Br9

Abstract A new high yield (75–95%) method—condensation of polyhedral clusters—for synthesis of octahedral rhenium cluster compounds Re 6 X 4 Br 10 and Re 6 X 8 Br 2 (X = S, Se, Te) has been developed using triangular cluster rhenium bromide Re 3 Br 9 and lead or cadmium chalcogenides as starting materials. The phases obtained were characterized by chemical analysis and X-ray powder diffraction method, and the cell unit parameters of compounds were found. The crystal structure of Re 6 Te 4 Br 10 was solved by X-ray single crystal analysis. Crystallographic data: triclinic, space group P 1, a = 9.347(2), b = 9.403(4), c = 13.348(4) A , α = 84.46(3), β = 84.64(2), γ = 82.11(2) °, V = 1152.8(6) A 3 , Z = 2, D x = 6.991 g-cm −3 , R(F) = 0.0378, wR(F 2 ) = 0.0906.

Molecular octahedral sulfido-bromide rhenium clusters: Synthesis and crystal structure of (PPh4)2[Re6S6Br8] ∗d CH3C6H5 and (PPh4)3[Re6S7Br7]

Abstract Two high-temperature (550°C) methods were used to prepare sulfido-bromide cluster complexes of rhenium; namely the reaction of Re3Br9 with PbS in the presence of KBr, and the reaction of Re6S4Br10 with KNCS. From the former reaction, a salt of [Re6S6Br8]2− has been obtained while the latter reaction gave a [Re6S7Br7]3− salt. X-ray structure determinations have shown both (PPh4)2[Re6S6Br8] ∗d CH3C6H5 and (PPh4)3 [Re6S7Br7] have Re6 clusters with bromine atoms at terminal positions. The face-capping positions are randomly occupied by sulfur and bromine atoms.

Complexes based on the anionic octahedral rhenium chalcogenide clusters and [M(En)2]2+ (M = Ni, Cu) cations

The compounds [Ni(H2O)2(En)2][{Ni(En)2}Re6S8(OH)6] · 7H2O (I), [{Cu(En)2}Re6S8(H2O)2(OH)4] · 4H2O (II), and [Ni(H2O)2(En)2]0.5[Re6Se8(H2O)3(OH)3] · 10H2O (III) were synthesized by layering aqueous solutions of Ni(En)2Cl2 or Cu(En)2Cl2 (En is ethylenediamine) onto aqueous solutions of the potassium salts of the corresponding octahedral chalcohydroxo rhenium cluster complexes [Re6Q8(OH)6]4− (Q = S, Se). The structure of the obtained compounds was determined by X-ray diffraction analysis.

Unexpected ligand substitutions in the cluster core {Re6Se8}: synthesis and structure of the novel cluster compound Cs11(H3O)[Re6Se4O4Cl6]3·4H2O

The compound Cs11(H3O)[Re6Se4(O)4Cl6]3.4H2O containing a novel cluster core {Re6Se4(O)4} with ordered ligands, where the 4 positions of one face of a Se4(O)4 cube are occupied exclusively by Se atoms and 4 O atoms lie in the opposite face was synthesized via the interaction of solid Re6Se8Br2 with molten KOH.

A morphotropic series of the cluster complexes [Ln(DMF)8][Re6Q7Br7] (Q = S, Se): Synthesis, structure, and thermal transformations

The reactions of the octahedral anionic complexes [Re6Q7Br7]3− (Q = S, Se) with lanthanide bromides in DMF were studied. The reactions gave a series of compounds [Ln(DMF)8][Re6Q7Br7] (Q = S, Se) containing [Ln(DMF)8]3+ complex cations. The compounds were studied by single-crystal and powder X-ray diffraction and thermal analyses. The crystal structures of [Ln(DMF)8][Re6S7Br7] with Ln = La (I), Ce (II), Nd (III), Eu (IV), and Lu (V) and [Ln(DMF)8][Re6Se7Br7] with Ln = La (VI), Ce (VII), Pr (VIII), and Lu (IX) were determined. It was found that [Ln(DMF)8][Re6Q7Br7] (Q = S, Se) can be divided into three structural groups: I, II, and VI (type A), VII (type B), and III–V, VIII, IX (type C). The complex [Pr(DMF)8][Re6Se7Br7] was found to crystallize in two polymorphous modifications with type B and C structures. Presumably, the morphotropic transitions in the [Ln(DMF)8][Re6Q7Br7] series (Q = S, Se) are mainly related to the change in the configuration of the [Ln(DMF)8]3+ cations, resulting in a change in the packing motif of large complex ions in the crystals. The compounds [Ln(DMF)8][Re6Se7Br7] decompose according to a stepwise pattern, which suggests an intermediate formation of the complexes [Ln(DMF)6][Re6Se7Br7] (this was proved for Ln = Yb, Lu) with subsequent more extensive transformations, which affect also the cluster anion.

First example of the cluster ammine complex [Re6Se7Br(NH3)6]3+: synthesis and structure of the [Re6Se7Br(NH3)6][Re6Se7BrBr6]·12H2O salt

The reaction of Cs3[Re6Se7BrBr6] with aqueous ammonia afforded the octahedral rhenium ammine cluster complex cation [Re6Se7Br(NH3)6]3+. This cation crystallized as the [Re6Se7Br(NH3)6][Re6Se7BrBr6]·12H2O compound. The crystal structure of this compound was established. The presence of the NH3 ligands in the coordination environment about the Re atom was confirmed by thermogravimetry, vibrational spectroscopy, and high-resolution mass spectrometry. The resulting compound is the first example of salts composed of the cluster cation and cluster anion possessing the same {Re6Se7Br} cluster core.

Synthesis and crystal structure of a new octahedral rhenium cluster compound Cs3Re6Se7Br7.H2O

Abstract New cluster compound Cs 3 Re 6 Se 7 Br 7 ·H 2 O was prepared and its crystal structure was solved by single crystal X-ray diffraction (XRD) analysis. Crystallographic data: triclinic, space group P 1, a = 9.613(2), b = 11.569(2), c = 13.344(3) A, α = 90.41(3), β = 95.48(3), γ = 106.48(3)°, V = 1415.6(5) A 3 , Z = 2, D x = 6.208 g·cm −3 , R (F) = 0.0400, w R (F 2 ) = 0.0882.

Crystal Structure of the Octahedral Cs4[Re6S8Br6] · 2H2O Cluster Complex

The octahedral Cs4[Re6S8Br6] cluster complex was obtained by the high‐temperature (850°) reaction of stoichiometric amounts of elemental substances (metallic rhenium, sulfur, bromine) in molten CsBr. Crystal hydrate of Cs4[Re6S8Br6]· 2H2O composition was isolated by recrystallization from an aqueous HBr solution. The crystal structure of the hydrate was determined by means of single‐crystal X‐ray structural analysis. The compound crystallizes in the hexagonal system with space group P63/mcm and unit cell parameters a = 9.762(1)Å, c = 18.763(2)Å, Vcell = 1548.5(3)3, Z = 2, dcalc = 5.192 g/cm3.

Coordinated bifluoride ions in the first thiofluoride molybdenum triangular cluster complex: synthesis and crystal structure of K5[MO3S4F7(FHF)2].2H2O

Abstract The first triangular thiofluoride cluster complex of molybdenum K 5 [Mo 3 S 4 F 7 (FHF) 2 ]·2H 2 O with unexpected coordination of bifluoride ions has been synthesized by the reaction of Mo 3 S 7 Br 4 with molten KHF 2 . The compound was characterized by single crystal X-ray diffraction. The compound crystallizes in the orthorhombic space group Cmc 2 1 with four formulas in unit cell of dimensions a=15.1060(20) A , b=8.7820(9) A , c=14.3358(13) A , V=1901.8(4) A 3 .