Remetalation processes upon the formation of magnetically active heterometallic sulfide-bridged clusters

The processes of formation of antiferromagnetic heterometallic trinuclear clusters Cp₂Cr₂(-SCMe₃)₂(₃-S)₂ML _n (ML _n = Re(CO)(NO), W(NO)₂, W(NO)Cl, and W(NO)(SCMe₃)) from the antiferromagnetic binuclear chromium(iii) complex Cp₂Cr₂(-SCMe₃)₂(-S) (1) and nitrosyl-containing halide derivatives of Re^I and W⁰ were considered. It is shown that adducts of1 with ML _m (ML _m = Re(NO)(CO)₂Cl₂, W(NO)₂C1₂·1, and W₂(NO)₂(CO)₄I₂) are formed at the first stage. Then they loose the CpCrHal₂ moiety and transform into the reactive remetalation products, CpCr((-SCMe₃)₂(-S)ML _x (M = Re and W). The latter complexes join the electron-deficient CpCrS moiety to generate triangular clusters. The magnetic behavior of antiferromagnetic adducts and triangular clusters is discussed, and the existence of correlations between the energy of spin-spin exchange (–2J(Cr-Cr)) and Cr-Cr and Cr-S(sulfide) bond lengths is mentioned.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 12, pp. 2337–2348, December, 1995.     

Formation of antiferromagnetic thiolate-bridged and sulfide-bridged complexes

Reactions of Cp₂Cr₂(SCMe₃)₂S (1) with rhenium complexes (CO)(NO)Re(PR₃)₂X₂ [R=Et, X=Cl (7a); R=Et, X=O₃SCF₃ (7b); R=OMe, X=O₃SCF₃ (7c)] containing strongly bound phosphine ligands and with Pd(PPrⁱ ₃)₂Cl₂ (8) containing bulky P donors were studied. The reaction between compounds1 and7a does not occur in various solvents within a temperature range of 22–80 °C. Interaction of1 with triflat derivatives7b and7c yields the paramagnetic tetrahedral homonuclear cationic cluster Cp₄Cr₄S₄ ⁺O₃SCF₃ ⁻ (10) and the binuclear methylated complex Cp₂Cr₂(SCMe₃)₂(SMe)⁺O₃SCF₃ ⁻ (11), respectively. The reaction of compound1 with8 affords the antiferromagnetic heteronuclear cluster Cp₂Cr₂(SCMe₃)S₂PdCl(PPrⁱ ₃) (12). The structure of the core of12 is analogous to the structures of the rhodium-containing complexes Cp₂Cr₂(μ-SCMe₃)(μ₃-S)₂RhL₂. Although compound8 reacts with Fe₃S₂(CO)₉ (5), the major products are the homometallic trinuclear clusters Fe₃S₂(CO)₈(PPrⁱ ₃) (14) (as a mixture of isomers) and Fe₃S₂(CO)₇(PPrⁱ ₃)₂ (15), whereas the heteronuclear complex (CO)₆Fe₂S₂Pd(PPrⁱ ₃)₂ (16) was found only in trace amounts. The reasons for the difference in the reactivities of the rhenium and palladium derivatives toward compounds1 and5 are discussed. The structures of complexes10 (two crystal modifications),11, 12, 15, and16 were established by X-ray structural analysis of the single crystals. For Part 4, see I. L. Eremenko, S. E. Nefedov, H. Berke, B. I. Kolobkov, and V. M. Novotortsev,Organometallics, 1995,14, 1132. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 141–152, January, 1997.     

Rhenium(IV) and rhenium(V) complexes with 3,5-dimethylpyrazole

Mono-and dinuclear Re^IV and Re^V complexes with 3,5-dimethylpyrazole (Me₂pzH) were synthesized. The cis-[Re₂O₃Cl₄(3,5-Me₂pzH)₄] complex (cis-1) was prepared by the reaction of NH₄ReO₄ with K[HB(Me₂pz)₃] in concentrated HCl or by refluxing of [ReCl₃(MeCN)(PPh₃)₂] with Me₂pzH in air. The bromide complex trans-[Re₂O₃Br₄(3,5-Me₂pzH)₄] (trans-2) was synthesized by passing dry HBr through a solution of [Re₂O₃Br₂(μ-3,5-Me₂pz)₂(3,5-Me₂pzH)₂] (4) in chloroform. The pyrazolate-bridged complex [Re₂O₃Cl₂(μ-3,5-Me₂pz)₂(3,5-Me₂pzH)₂] (3) was prepared from (Et₄N)₂[ReOCl₅] or Cs₂[ReOCl₅] and Me₂pzH. The corresponding bromide and iodide complexes [Re₂O₃X₂(3,5-Me₂pz)₂(3,5-Me₂pzH)₂] · C₆H₆ (X = Br (4) or I (5)) were synthesized by the reactions of (NH₄)₂[ReBr₆] or K₂[ReI₆], respectively, with Me₂pzH. The [ReO(OMe)(3,5-Me₂pzH)₄]Br₂ · · 3,5-Me₂pzH · 4H₂O complex (6) was obtained as a by-product in the synthesis of complex 4. The reaction of [ReNCl₂(PPh₃)₂] with Me₂pzH was accompanied by hydrolytic denitration giving rise to the mixed-ligand complex [Re₂O₃Cl₂(μ-3,5-Me₂pz)₂(3,5-Me₂pzH)(PPh₃)] (7). The reaction of (NH₄)₂[ReBr₆] with a Me₂pzH melt gave the trans-[ReBr₄(3,5-Me₂pzH)₂] · · Me₂CO complex (8). The structures of complexes 2 and 4–8 were established by X-ray diffraction. All compounds were characterized by elemental analysis, electronic absorption spectroscopy, ¹H NMR and IR spectroscopy, mass spectrometry, and cyclic voltammetry. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 52–59, January, 2006.     

First molecular octahedral rhenium cluster complexes with terminal As- and Sb-donor ligands

Six new molecular octahedral cluster complexes with the general formulas trans-[{Re₆(μ₃-Q)₈}(EPh₃)₄Br₂] and fac-[{Re₆(μ₃-Q)₇(μ₃-Br)}(AsPh₃)₃Br₃] (Q = S or Se and E = As or Sb) were synthesized by the reactions of the cesium salts of the [{Re₆(μ₃−S)₈}Br₆]⁴⁻, [{Re₆(μ₃-Se)₈Br₆]³⁻, and [{Re₆(μ₃-Q)₇(μ₃-Br)}Br₆]³⁻ anions with molten triphenylarsine (AsPh₃) and triphenylantimony (SbPh₃), respectively. The compositions and structures of the resulting complexes were established by single-crystal X-ray diffraction and confirmed by elemental analysis and vibrational spectroscopy. The compositions and structures of the complexes depend on the composition of the cluster core in the starting salts. The luminescence spectra were recorded for powdered samples of all these compounds and the earlier described complexes trans-[{Re₆Q₈}(PPh₃)₄Br₂] and fac-[{Re₆Q₇Br}(PPh₃)₃Br₃]. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1614–1619, August, 2008.     

Modern aspects on tri- and tetranuclear cluster complexes supported by phosphido bridges

This report on small cluster complexes with metal-metal bonds in the field of coordination chemistry documents results in the following scientific areas. (1) Systematic synthetic routes via ditransition metal carbonyl derivative of manganese and rhenium (group 7) to functionalizedtriangulo- andtetrahedro-clusters including structural characterization, (2) Dynamic properties of mono- and diauration isomers like M₂(μ-AuPR₃)(μ-PCyH)(CO)₈/M₂(μ-H)(μ₃-PCy(AuPR₃))(CO)₈ (isomerization) and M₂(μ-AuPR₃)₂(μ₄-PCy)(CO)₈/M₂(μ-AuPR₃)(μ₃-PCy(AuPR₃))(CO)₈ (M = Mn, Re; R = organic residue) (rearrangement and valence isomerization) and MM’(μ-H)(μ-PCy₂)(μ₄-PCy(AuPR₃))(CO)₆ (M = M’, M ≠ M’) (topomerization) going from one to the other homologue and the kinetic study of isomerization in the framework Re₂(AuPCy₃)₂(μ-PMeN₂(μ-C(Bu)O)(CO)₆, (3) Correlations of chirality transfer in diastereomerictetrahedro-clusters Re₂(M¹PR₃)₂(μ-PCy₂)(CO)₇(η¹-L*) (M¹ = coin metals, L* = chiral ligand as (+) or (-) prolinate, for example) from CD data. These selected contributions will be discussed to answer the question “Do small cluster complexes remain as a future challenge in cluster chemistry?”     

Dirhenium Compounds Supported by <Emphasis Type="Italic">N</Emphasis>,<Emphasis Type="Italic">N</Emphasis><Emphasis Type="BoldItalic">′</Emphasis>-Dimethylbenzamidinate: Formation of Linear Polymers via Axial Ligation

The reaction between Re₂(DMBA)₄Cl₂ and NaN(CN)₂ resulted in Re₂(DMBA)₄(N(CN)₂)₂ (1a), where DMBA is N,N′-dimethylbenzamidinate. Molecular compounds Re₂(DMBA)₄(ReO₄)₂ (1b) and Re₂(DMBA)₄(OP(O)(OH)Ph)₂ (1c) were obtained through the reactions between Re₂(DMBA)₄(NO₃)₂ and the respective monoanion. The dirhenium(III) coordination polymers [Re₂(DMBA)₄(μ-O,O′-WO₄)·2H₂O]_∞ (2a), [Re₂(DMBA)₄(μ-O,O′-MoO₄)·2H₂O]_∞ (2b), and [Re₂(DMBA)₄(μ-O,O′-1,4-(O₂C)₂C₆H₄)·2H₂O]_∞ (2c) were similarly prepared through slow diffusion of Re₂(DMBA)₄(NO₃)₂ in acetonitrile into aqueous solution containing the respective dianion. All new compounds were characterized with single crystal X-ray diffraction, which revealed the retention of the essential structural features of Re₂(DMBA)₄ unit upon the formation of coordination polymers.     

Lanthanide-Organic Frameworks Based on {Ln<Subscript>4</Subscript>(μ<Subscript>3</Subscript>-OH)<Subscript>4</Subscript>(μ<Subscript>2</Subscript>-OH)<Subscript>2</Subscript>} Cluster Units

Abstract  

Three novel lanthanide-organic frameworks: [Ln₂(pyba)₃(μ₃-OH)₂(μ₂-OH)(H₂O)] _n (Ln = Er (1), Y (2), Dy (3) Hpyba = 4-pyridin-4-yl-benzoic acid) have been hydrothermally synthesized and structurally characterized by single crystal X-ray diffraction. Structure analysis shows that each {Ln₄(μ₃-OH)₄(μ₂-OH)₂} cluster units interconnect to form 1-D chains, which are further linked by π–π interactions to make a 3-D supramolecular network structure. Furthermore, the IR, PXRD and TGA of compounds 1–3 were also studied.     

Reactions of the Dirhenium(II) Complexes Re2X4(μ-dppm)2 (X=Cl, Br; dppm=Ph2PCH2PPh2) with Isocyanides. XXII. A Comparison of Mixed Carbonyl–Isocyanide Complexes with Those Formed by Re2Cl4(μ-dcpm)2 (dcpm=Cy2PCH2PCy2)

The reactions of the electron-rich triply bonded dirhenium(II) complex Re₂Cl₄(-dcpm)₂ (dcpm=Cy₂PCH₂PCy₂) with the isocyanide ligands XylNC (Xyl=2,6-dimethylphenyl) and t-BuNC afford the complexes Re₂Cl₄(-dcpm)₂(CNXyl) and Re₂Cl₄(-dcpm)₂(CN-t-Bu)₂ which in turn react with CO to give salts of the [Re₂Cl₃(-dcpm)₂(CO)₂(CNXyl)]⁺ and [Re₂Cl₃(-dcpm)₂(CN-t-Bu)₂(CO)]⁺ cations which exist in different isomeric forms. This chemistry is compared with that developed previously for the analogous complexes derived from Re₂Cl₄(-dppm)₂.     

Study of allylic rearrangement in (μ-H)Os3(μ-O=CNRCH2CH=CH2)(CO)10 (R=H or CH3) clusters

The migration of the double bond in the allylcarboxamide ligands of (μ-H)Os₃(μ-O=CN RCH₂CH=CH₂) (CO)₁₀ (R=H (1) or CH₃ (2)), (μ-D)Os₃(μ-O=CNDCH₂CH=CH₂) (CO)₁₀, and (μ-H)Os₃(μ-O=CNHCD₂CH=CH₂)(CO)₁₀ clusters was studied by¹H,²H, and¹³C NMR spectroscopy. Neither μ-D nor ND groups in the deuterated complexes are directly involved in prototropic processes of allylic rearrangement. Initially, the deuterium atom of the CD₂ group migrates to the ψ-carbon atom of the allyl fragment to form the −CD=CH-CH₂D propenyl moiety, in which the deuterium and hydrogen atoms are gradually redistributed between the ψ-and β-carbon atoms. The triosmium cluster complexes containing the bridging carboxamide ligands O=CNRR' catalyze the allylic rearrangement ofN-allylacetamide. Based on the data obtained, the probable scheme of the allylic rearrangements in clusters1 and2 was proposed. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 2182–2186, November, 1999.     

Crystal structure of a tetrahedral cluster complex [Zn2(NH3)6(μ-OH)][Zn(NH3)4]0.5[Re4Te4(CN)12]·5H2O

A cluster complex of the composition [Zn₂(NH₃)₆(μ-OH)][Zn(NH₃)₄]_0.5[Re₄Te₄(CN)₁₂]·5H₂O is obtained by the interaction of an aqueous solution of K₄[Re₄Te₄(CN)₁₂]·5H₂O with an aqueous ammonia solution of ZnCl₂. The compound crystallizes in the C2/m (12) monoclinic space group with unit cell parameters a = 23.233(2) ?, b = 14.5906(16) ?, c = 14.3825(15) ?, β = 125.169(1)°, V = 3985.5(7) ?³, Z = 4, d _x = 3.290 g/cm³. The structure is built from cluster [Re₄Te₄(CN)₁₂]⁴⁻ anions and complex [Zn₂(NH₃)₆(μ-OH)]³⁺ and [Zn(NH₃)₄]²⁺ cations; the latter is disordered over two positions.     

Reaction of Os3(μ-Cl)2(CO)10 with Ph2PCH2PPh2. The formation of a novel 12-membered macrocycle containing C, P, Cl, and Os atoms in the ring

The reaction of Os₃(μ-Cl)₂(CO)₁₀ (1) with Ph₂PCH₂PPh₂ (dppm) in a toluene solution at 65°C results in novel osmium complexes [Os₃(μ-Cl)₂(CO)₉]₂(dppm) (2) and [Os₃(μ-Cl)₂(CO)₈]₂(dppm)₂ (3). Compounds 2 and 3 were characterized by¹H and³¹P NMR, and IR spectroscopy and their structures were established by X-ray analysis. In both compounds, dppm is a bridging ligand between the two cluster units. Molecule3 can be considered as an unusual 12-membered macrocycle containing C, P, Cl, and Os atoms in the ring. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1844–1851, September, 1998.     

New cobalt and iron pivalate complexes with 2,2′:6′,2″-terpyridine: synthesis, structure, and magnetic properties

The mononuclear complexes (η³-terpy)M(Piv)²·MeCN (M = Fe ⁱⁱ (3) and Co ⁱⁱ (4), and Piv is the pivalate anion) were synthesized by the reactions of polymeric iron(ii) and cobalt(ii) pivalates with 2,2′:6′,2″-terpyridine (terpy). The oxidation of compound 3 affords the pentanuclear heterospin iron(ii,iii) complex (η³-terpy)Fe₅(μ₄-O)(μ₃-OH)(μ-OH)₂(μ-Piv)₇(η¹-Piv)₂ (5). All compounds were characterized by X-ray diffraction. Dedicated to the 90th anniversary of the L. Ya. Karpov Institute of Physical Chemistry. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1186–1190, June, 2008.     

New polynuclear cobalt trimethylacetate complexes: synthesis and structure

Extraction of polymer (1), formed in the reaction of CoCl₂ with KOOCBu^t, with boiling hexane gives crystals of hexamer Co₆(μ₃-OH)₂(OOCBu¹)₁₀(HOOCBu¹)₄ (2). According to data of X-ray study, four Co¹¹ atoms in the hexanuclear molecule2 have an octahedral ligand environment and two Co¹¹ atoms have a tetrahedral one. Dissolution of polymer1 in EtOH results in its splitting into Co₄(μ₃-OH)₂(OOCBu¹)₆(HOEt)₆ tetramers (3). In molecule3, two asymmetric dimeric (η²-OOCBu^t)(EtOH)Co(μ-OOCBu^t)Co(HOEt)₂ fragments are bound by two tridentate bridging OH groups. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1773–1778, September, 1999.     

Crystal structures of the octahedral rhenium cluster compexes Cs4[Re6S8(OH)6]·6H2O and Cs4[Re6Se8(OH)6]·8H2O

The salts Cs₄[Re₆S₈(OH)₆]·6H₂O (1) and Cs₄[Re₆Se₈(OH)₆]·8H₂O (2) were obtained by the reactions of Re₆S₈Br₂ and Re₆Se₈Br₂ with a CsOH melt with further solution of the products in water and crystallization of 1 and 2 from the aqueous solutions. The structure of the compounds was established by X-ray single crystal diffraction analysis. Compound 1 crystallizes in the orthorhombic space group Pbca with unit cell parameters a = 14.175(2) Å, b = 11.321(2) Å, c = 17.503(2) Å, V = 2808.5(7) ų, Z = 4, d _calc = 5.003 g/cm³; compound 2 crystallizes in the triclinic space group with unit cell parameters a = 9.020(4) Å, b = 9.127(4) Å, c = 10.289(4) Å, α = 79.589(7)°, β = 75.829(7)°, γ = 72.186(7)°, V = 776.8(6) ų, Z = 1, d _calc = 5.402 g/cm³. Original Russian Text Copyright ? 2007 by K. A. Brylev, Yu. V. Mironov, S.-J. Kim, and V. E. Fedorov __________ Translated from Zhurnal Strukturnoi Khimii, Vol. 48, No. 6, pp. 1183–1188, November–December, 2007.     

Preparation and Structures of Several Complexes Containing Carbon-Rich Ligands Attached to Polynuclear Metal Carbonyls

Several new gold-containing cluster complexes have been prepared from the reactions of gold alkynyl complexes, L _n M-C _x -Au(PPh₃), (x = 3, 4, 6) with Ru₃(CO)₁₀(NCMe)₂. The bis-cluster complex 1,4-{AuRu₃(CO)₉(PPh₃)(μ₃-C₂)}₂C₆H₄ was obtained from Ru₃(CO)₁₀(NCMe)₂ and 1,4-{(Ph₃P)Au(C≡C)}₂C₆H₄. The complexes Ru₃(μ-H){μ₃-C₂C≡C[Ru(PP)Cp′]}(CO)₉ [PP = (PPh₃)₂, Cp′ = Cp; PP = dppe, Cp′ = Cp*] were also obtained as minor by-products and synthesised independently from Ru(C≡CC≡CH)(PP)Cp′. A reaction between Co₃{μ₃-CC≡CC≡CAu(PPh₃)}(μ-dppm)(CO)₇ and Ru₃(CO)₁₂ afforded {(Ph₃P)(OC)₉AuRu₃}C≡CC≡CC{Co₃(μ-dppm)(CO)₇} 7. Related complexes AuRu₃{μ₃-C₂C≡[M(CO)₂Tp]}(CO)₉(PPh₃) (M = Mo 8, W 9) were obtained from {Tp(OC)₂M}≡CC≡C{Au(PPh₃)}, while the mixed metal cluster complexes MoM₂(C₂Me)(CO)₈Tp (M = Ru 13, Fe 14) were obtained from M(≡CC≡CSiMe₃)(CO)₂Tp (M = Mo, W) with Fe₂(CO)₉ and Ru₃(CO)₁₂, respectively. Reactions of the Mo carbyne complex with Co₂(LL)(CO)₆ [LL = (CO)₂, μ-dppm] or nickelocene afforded complexes 15–17 in which Co₂ and Ni₂ fragments, respectively, had coordinated to the C≡C triple bond. XRD structural determinations of 7, 8, 14, 16 and {Tp(OC)₂W}≡CC≡CC≡{Co₃(μ-dppm)(CO)₇} (18-W) are reported. In memoriam: F. Albert Cotton (1930–2007).     

Zn(II) and Cu(II) Complexes with the Cluster-based Ligand [Re6(μ 3-Se)8(PEt3)5(PTA)](SbF6)2 (PTA = 1,3,5-Triaza-7-phosphaadamantane)

Zn(II) and Cu(II) complexes of the cluster-based ligand [Re₆(μ ₃-Se)₈(PEt₃)₅(PTA)](SbF₆)₂ (PTA = 1,3,5-triaza-7-phosphaadamantane), {Zn[Re₆(μ ₃-Se)₈(PEt₃)₅(PTA)](NO₃)₃}(SbF₆) (1) and {Cu[Re₆(μ ₃-Se)₈(PEt₃)₅(PTA)](NO₃)₃}(SbF₆) (2), were prepared and structurally characterized. They are the first N-coordinated Zn(II) and Cu(II) complexes wherein the PTA ligand displays an interesting and less-frequently observed P, N-coordination mode. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Coordination compounds based on the cluster anion [Re4Te4(CN)12]4− and Zn2+ cation

Three new coordination compounds [{Zn(H₂O)₂} {Zn(H₂O)₄} Re₄Te₄(CN)₁₂] (1), [Zn(en)₂(NH₃)₂][{Zn(en)(NH₃)₂} Re₄Te₄(CN)₁₂]·H₂O (2), and [{Zn₂(dien)₃} Re₄Te₄(CN)₁₂]· ·₆H₂O (3) (dien is diethylenetriamine) were prepared by reactions of aqueous solutions of the tetrahedral cluster rhenium tellurocyanide complex K₄[Re₄Te₄(CN)₁₂]· 5H₂O with zinc dichloride in the presence of ammonia, ethylenediamine, and diethylenetriamine, respectively. Complex 1 has a three-dimensional structure with two types of the Zn atoms; complex 2 is ionic with the polymeric chain anion; complex 3 has a molecular structure. The structures of complexes 1–3 were determined by single-crystal X-ray diffraction analysis. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 4, pp. 718–721, April, 2006.     

Synthesis and Characterizations of Ferrocenyl Carbonyl Chromium and Cobalt Clusters

Two novel bimetallic complexes, [Cr(CO)₃(η ⁶-C₆H₅)–C≡C–C₆H₄–Fc] (Fc = C₅H₅FeC₅H₄] (1) and [Cr(CO)₃(η ⁶-C₆H₅)–C ≡ C–Fc–C(CH₃)₂–Fc] (3), were synthesized by the Sonogashira coupling reaction. By using of (1) and (3) as ligands to react with Co₂(CO)₈, two others novel polymetallic complexes, [Cr(CO)₃(η ⁶-C₆H₅){Co₂(CO)₆-η ²-μ ²-C≡C–}–C₆H₄–Fc] (2) and [Cr(CO)₃(η ⁶-C₆H₅){Co₂(CO)₆-η ²-μ ²-C≡C–}Fc–C(CH₃)₂–Fc] (4) were obtained. Four carbonyl complexes were characterized by elemental analysis, FT-IR, NMR and MS. The molecular structures of complexes (1), (2) and (4) were determined by single crystal X-ray diffraction. The interactions among the ferrocenyl, Cr(CO)₃ and Co₂(CO)₆-η ²-μ ²-C≡C– units were investigated by cyclic voltammetry.     

Pivalate Bridged High Spin Manganese(II) and Iron(II) Polymers

Antiferromagnetic Mn(II) polymers of general formula {[L₂Mn(μ-OOCCMe₃)₂][Mn₂(μ-OOCCMe₃)₄]}_n (L = 1,2-phenylenediamine (3) and 4,5-dimethyl-1,2-phenylenediamine (4)) were synthesized from [Mn(μ-OOCCMe₃)₂(HOEt)] _n (1) polymer and arenediamines in MeCN solution. The tetranuclear cluster Fe₄(μ₃-OH)₂(μ-OOCCMe₃)₄(η²-OOCCMe₃)₂(EtOH)₆ (5) was prepared by reacting FeSO₄·7H₂O with KOOCCMe₃ in EtOH and was used as starting pivalate iron(II) agent in further reactions. The thermolysis of 5 in MeCN was shown to result in a ferromagnetic polymer [Fe(μ-OOCCMe₃)₂] _n (6) containing tetrahedral iron(II) atoms. Cluster 5 was found to react with o-phenylenediamine giving rise to ferrimagnetic polymer [Fe(μ-OOCCMe₃)₂(HOEt)]_n (7). The reaction 7 with 2,6-diaminopyridine in MeCN results in binuclear antiferromagnetic complex (2,6-(NH₂)₂C₅H₃N)₂Fe₂(μ-OOCCMe₃)₄· 4MeCN (8). However the reaction of 4,5-dimethyl-1,2-phenylenediamine with polymer 7 yields a polymer {[L₂Fe(μ-OOCCMe₃)₂][Fe₂ (μ-OOCCMe₃)₄]} _n (9), which is an analogue of the manganese polymer 4. All newly synthesized compounds were characterized by the by X-ray diffraction studies and magnetic measurement. Dedicated to Professor Ilya I. Moiseev in recognition of his outstanding contribution to cluster chemistry     

Structure of complex salts [Co(NH3)6][Rh(NO2)6] and [Co(NH3)6][(NO2)3Rh(μ-NO2)1+x(μ-OH)2?xRh(NO2)3]·(2-x)(H2O), x = 0.17

The structures of two salts [Co(NH₃)₆][Rh(NO₂)₆] (I) and [Co(NH₃)₆][(NO₂)₃Rh(μ-NO₂)_1+x (μ-OH)_2−x Rh(NO₂)₃]·(2−x)(H₂O), x = 0.17 (II) are solved. Single crystals of the salts are obtained by the counter diffusion method through the gel of aqueous solutions of [Co(NH₃)₆]Cl₃ and Na₃[Rh(NO₂)₆]. The structure of [Co(NH₃)₆][Rh(NO₂)₆] is consistent with the diffraction data for a polycrystalline sample of poorly soluble fine salt formed in the exchange reaction between aqueous solutions of [Co(NH₃)₆]Cl₃ and Na₃[Rh(NO₂)₆]. The structure of [Co(NH₃)₆][(NO₂)₃Rh(μ-NO₂)_1+x (μ-OH)_2−x Rh(NO₂)₃]·(2−x)(H₂O), x = 0.17 exhibits the stabilizing effect of a large cation in the formation of novel, unknown previously coordination ions: [(NO₂)₃Rh(μ-NO₂)(μ-OH)₂Rh(NO₂)₃]³⁻ and [(NO₂)₃Rh(μ-NO₂)₂(μ-OH)Rh(NO₂)₃]³⁻.