Synthesis and structure investigation of Co(III) complex salts with the perrhenate anion

Abstract

Complex salts of the composition [Co(NH 3 ) 6 ](ReO 4 ) 3 ⋅2H 2 O (I), [Co(en) 3 ](ReO 4 ) 3 (II), [Co(NH 3 ) 5 H 2 O](ReO 4 ) 3 ⋅2H 2 O (III), and [Co(NH 3 ) 5 Cl](ReO 4 ) 2 ⋅0.5H 2 O (IV) are obtained. Their crystal structures are determined by single crystal XRD. Crystallographic characteristics: (I) a = 9.9797(3) Å, b = 12.6994(3) Å, c = 14.7415(4) Å, β = 102.870(1)°, C2/c space group; (II) a = 8.0615(3) Å, b = 8.4483(4) Å, c = 8.8267(4) Å, α = 61.923(2)°, β = 89.552(2)°, γ = 72.295(2)°, P1 space group; (III) a = 8.0086(4) Å, b = 12.9839(6) Å, c = 17.5122(7) Å, β=91.858(1)°, P2 1 /n space group; (IV) a = 14.9446(3) Å, b = 14.6562(4) Å, c = 12.2434(4) Å, Cmc2 1 space group. Compounds consisting of complex cations and anions (double complex salts) are considered as precursors of various nanoscale bimetallic powders [1, 2]. Complex salts in which one of the metals is rhenium are of interest, in particular, the compounds in which the cationic part is a complex ion of any metal and the anionic part consists of the perrhenate ion. Therefore, complex compounds of the composition [M(NH 3 ) 5 Cl](ReO 4 ) 2 , where M = Ir, Rh, Ru, Cr, Co [3], [M(NH 3 ) 4 ](ReO 4 ) 2 (M = Pd, Pt) [4, 5], [Pt(NH 3 ) 5 Cl](ReO 4 ) 3 ⋅2H 2 O [6], [Au(dien)Cl](ReO 4 ) 2 , where dien is diethylenetriamine C 4 H 13 N 3 [7] have previously been studied.The purpose of this work is to synthesize and structurally investigate some amine complexes of cobalt(III) with a ratio Co:Re = 1:3, such as [Co(NH 3 ) 6 ](ReO 4 ) 3 ⋅2H 2 O (I), [Co(en) 3 ](ReO 4 ) 3 (II), where en is ethylenediamine C 2 Н 8 N 2 , [Co(NH 3 ) 5 H 2 O](ReO 4 ) 3 ⋅2H 2 O (III), and also to determine the crystal structure of [Co(NH 3 ) 5 Сl](ReO 4 ) 2 ⋅0,5H 2 O (IV) (metal ratio is 1:2). For the first time, compound IV was obtained in the synthesis of a series of complex compounds [M(NH 3 ) 5 Cl]× (ReO 4 ) 2 , where M = Ir, Rh, Ru, Cr, Co [3]. However, the diffraction pattern of the polycrystalline sample was indexed using the structural data for [Rh(NH 3 ) 5 Cl](ReO 4 ) 2 complex salt, and their isostructurality was established. The description of the crystal structure of [Co(NH 3 ) 5 Сl](ReO 4 ) 2 ⋅0.5H 2 O (IV) determined by single crystal XRD is given in the present work. EXPERIMENTAL In the work, we used NaReO 4 (chemically pure), [Co(en) 3 ]Cl 3 [8], [Co(NH 3 ) 5 Cl]Cl 2 , and [Co(NH 3 ) 6 ]Cl 3 [9] complexes obtained by the known procedures.

An unexpected rhenium(IV)–rhenium(VII) salt: [Co(NH3)6]3[ReVIIO4][ReIVF6]4·6H2O

“…In the tetrahedral [ReO 4 ] À anion in (I), the average Re-O bond length (1.719 Å ) is in agreement with the average Re-O bond length of 1.720 Å in [Co(NH 3 ) 6 ](ReO 4 )Á2H 2 O (Baidina et al, 2012). In (I) the values of three Re-O bond lengths, [Re1-O2 i , Re-O2 and Re-O2 ii = 1.715 (8) Å ; symmetry codes: The molecular structure of (I) showing displacement ellipsoids drawn at the 50% probability level for all non-H atoms.…”

“…The octahedral [Co(NH 3 ) 6 ] 3+ cation in (I) is slightly distorted; the average Co-N bond length of 1.962 Å is in agreement with the average Co-N bond lengths of 1.963 Å in [Co(NH 3 ) 6 ](ReO 4 )Á2H 2 O (Baidina et al, 2012) and 1.966 Å in [Co(NH 3 ) 6 ](TcO 4 ) 3 (Poineau et al, 2017). In (I), the shortest CoÁ Á ÁCo and NÁ Á ÁN separations between nearby [Co(NH 3 ) 6 ] 3+ cations are 7.035 (1) and 4.473 (1) Å , respectively.…”

Multi-Centered Solid-Phase Quasi-Intramolecular Redox Reactions of [(Chlorido)Pentaamminecobalt(III)] Permanganate—An Easy Route to Prepare Phase Pure CoMn2O4 Spinel

“…Unfortunately, this reaction route cannot be used to prepare compound 3-Mn due to the spontaneous reaction between the permanganate ions and the HCl solution (chlorine evolution and Mn II formation). Therefore, a chloride ion has to be introduced into the inner coordination sphere of the cobalt in the absence of a permanganate ion-for example, with the preparation of [Co(NH 3 ) 5 Cl]Cl 2 (compound 4) [14]-and the outer sphere chloride ions have to be exchanged with permanganate ions, such as occurred with the perrhenate ions in the preparation of compound 3-Re [15,16]. A possible reaction route is the reaction of [Co(NH 3 ) 5 Cl]SO 4 [14] with barium permanganate [17][18][19][20]; however, this method was not used due to the relatively low solubility of compound 3-Mn in water that causes problems in the separation of compound 3-M from the insoluble barium sulfate by-product.…”

“…The powder X-ray diffractogram calculated from the SXRD data agreed very well with the experimentally determined powder X-ray diffractogram (Figure S1). Crystallographic data, details of the structure and the refinement results are listed in Table 2, together with the data obtained for the analog perrhenate complex (compound 3-Re) [15]. The structural features of compound 3-Mn are shown in Figures 1-3.…”

[Ru(NH3)6](MoO4)Cl·3H2O and [M(NH3)6](ReO4)3·2H2O (M = Ru, Ir). Synthesis and crystal structure

“…It is found that synthesized [M(NH 3 ) 6 ](ReO 4 ) 3 ⋅2H 2 O (М = Ru, Ir) salts are isostructural to the previously studied phases with М = Со [22] and Rh [23]. Crystallographic data for the salts of this series are summarized in Table 1.…”