Cadmium bis(phenylselenolate) as a precursor for the synthesis of polymeric Cd(μ-Se)clusters: Crystal and molecular structures of [Cd4(SePh)7(PPh3)X] (X = Cl, Br)

Synthesis and characterization of [Cd8Cl2Se(SePh)12(PCy3)2]·2.5CH3OH

“…Since these methods in general can also be applied to the synthons of the general formula M(ER) n , for which the examples M = Mg, Bi, Ga, In, Sn, Sb, Zn, Cd, Hg, Au, Yb, Zr, Hf; E = S, Se, Te; R = aryl, alkyl, have been reported, 29 we can also predict that a systematic methodology for the synthesis of binary and ternary clusters should be possible. [30][31][32][33][34][35][36][37][38][39][40][41][42] The formation of the final product -small clusters (26, 27), one-dimensional chains (24, 25, 28), or large clustersdepends on the reactivity of the synthon used. The greater is the reactivity of the synthon, the larger the resulting cluster.…”

“…[30][31][32][33][34][35][36][37][38][39][40][41][42] We have explored these reactions with Hg(ER) 2 in coordinating solvents to prepare a series of Hg-Te, Hg-Se and Ag-Te-Hg clusters (see compounds 1-23 in Scheme 1). Recently, Cd(SePh) 2 has been also used in the formation of some cadmium organochalcogenolate complexes [Cd 4 (SePh) 7 XPPh 3 ] n (X = Cl, Br) 30 and [Cd 2 (SePh) 2 X 2 (PCy 3 ) 2 ] (X = Br, I; PCy 3 = tricyclohexylphosphine) 42 under solvothermal conditions (stainless steel sealed reactor at 130 °C). Solvothermal synthesis was useful for the growth of crystals suitable for X-ray structure determination since the crystals grow slowly over the course of hours to days.…”

“…The thermogravimetric data agree with the X-ray diffraction results for the molecular structure of the compound, and is similar to the clusters [Cd 4 (SePh) 7 (PPh 3 )X] n (X = Cl, Br) which we have investigated previously. 30 Figure 6 displays the UV-Vis absorption spectrum of [Cd 8 Cl 2 (µ 4 -Se)(SePh) 12 (PCy 3 ) 2 ] as a nujol mull at Vol. 21, No.…”

“…[38][39][40] More recently we have found out that a critical step to develop new clusters under controlled conditions is the adequate understanding of the processes which lead to the stabilization and isolation of species like PhEMX (M = Cd, Hg; E = Se, Te; X = Cl, Br, I). In order to demonstrate these procedures and to extend the applicability of this methodology to further examples, we reported the preparation and the structural characterization of a series of cluster molecules [Cd 4 (SePh) 7 XPPh 3 ] n (X = Cl, Br) 30 [Hg 2 X 2 (SePh) 2 (PCy 3 ) 2 ] (X = Cl, Br), 41 [Cd 2 (SePh) 2 X 2 (PCy 3 ) 2 ] (X = Br, I; PCy 3 = tricyclohexylphosphine), 42 as well as the polymeric cluster [{Hg 5 Br 3 (TePh) 7 } n ] 41 and [Cd 4 (SePh) 7 Br(PCy 3 )]n (PCy 3 = tricyclohexylphosphine). 42 Finally, with the aim to expand the applicability of new synthetic routes to attain larger clusters, as well as to contribute to the knowledge on the properties and structural features of new materials based in our previous experience (an overview about our previous results is presented in Scheme 1), we describe in this work the synthesis, the structural characterization and the electronic (UV-Vis) spectra of the new cluster [Cd 8 …”

“…We have already reported some results about the influence of ligands, coordinating solvents and reaction stoichiometry in the size and stereochemistry of different cluster compounds. [30][31][32][33][34][35][36][37] Our studies have been extended to investigate new synthetic routes to produce either binary or ternary clusters, such as the reactions of Hg(TePh) 2 with M′-salts (M′ = Ag I , Co II , Ni II ), stabilized by phosphines (PPh 3 or P(CH 3 ) 2 Ph) and pyridine. [38][39][40] More recently we have found out that a critical step to develop new clusters under controlled conditions is the adequate understanding of the processes which lead to the stabilization and isolation of species like PhEMX (M = Cd, Hg; E = Se, Te; X = Cl, Br, I).…”