Zum Mechanismus des thermischen Abbaus von Ammonium- und Ammin-Chlorokomplexen des Rutheniums,Rhodiums, Palladiums und Platins

On the Mechanism of the Thermal Decomposition of Ammonium and Ammin Chloro Complexes of Ruthenium, Rhodium, Palladium and Platinum The thermolysis of noble metal compounds was investigated by a combination of independent physical (DTA/TG, high-temperature Guinier-Simon-technique) and preparative methods, characterization of the educts, intermediats and products by Guinier X-ray patterns and IR spectroscopy:

• (a) (NH₄)₂[PtCl₆], (NH₄)₂[PtCl₄], [Pt(NH₃)₄][PtCl₄], [Pt(NH₃)₄]Cl₂, and trans-[Pt(NH₃)₂Cl₂];
• (b) (NH₄)₂[PdCl₄], [Pd(NH₃)₄]Cl₂, trans-[Pd(NH₃)₂Cl₂], and [Pd(NH₃)₄][PdCl₄];
• (c) (NH₄)₂[RhCl₅(H₂O)], (NH₄)₃[Rh₂Cl₉], K₂[RhCl₅(H₂O)], and K₂[RhCl₅(NH₃)];
• (d) (NH₄)₂[RuCl₅(NH₃)] and (NH₄)₄[Ru₂Cl₁₀O]

. The most important step of the mechanism of the thermal decomposition is the ?internal”? redox reaction between the noble metal cation and the nitrogen atom of the ammine ligand.     

Über Chalkogenolate. LIV. Untersuchungen über Thioameisensäuren 2. Darstellung und Eigenschaften von Dithioformiaten

K[HCS₂] was prepared by interaction of chloroform with K₂S. Rb[HCS₂] and Cs[HCS₂] were formed by reaction of trimeric dithioformic acid with alcoholates (X-ray data see ?Inhaltsübersicht”?). The dithioformates T1[HCS₂], In[HCS₂]₃, and M[HCS₂]₂ with M = Pb, Zn, Cd, Hg, and M[HCS₂] with M = [(C₆H₅)₄P], [(C₆H₅)₄As], [(C₂H₅)₄N], (C₆H₅)₃Sn have been prepared. The prepared compounds are investigated by different methods.     

Organotin(IV) isothiocyanatochromates

Summary Several new compounds of the type [R₃Sn]₃[Cr(NCS)₆] and [R₃Sn][Cr(NCS)₄L₂], where R = Ph or n-Bu and L = NH₃, PhNH₂ or CO(NH₂)₂, have been synthesized and characterized by analytical data, i.r. and electronic spectral studies. Conductance measurements indicate that the compounds are ionic.     

Anwendung von Thionol, Thionolin und Thionin als titanometrische Indicatoren

Zusammenfassung Die Verbindungen Thionol, Thionolin und Thionin sind als Indicatoren für visuelle Titrationen mit Titan(III) unter den in der Arbeit angegebenen Bedingungen geeignet. Die Ergebnisse der Titration von K₂Cr₂O₇, FeCl₃, AuCl₃, NH₄VO₃, H₂[PtCl₆], K₃[Fe(CN)₆] und OsO₄ sind angegeben.

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Summary Conditions have been worked of for the application of thionol, thionoline, and thionine as indicators in visual titrations with titanium(III). Results of the determinations of K₂Cr₂O₇, FeCl₃, AuCl₃, NH₄VO₃, H₂[PtCl₆], K₃[Fe(CN)₆] and OsO₄ have been presented.

     

Darstellung und Kristallstruktur von (NH4)2[V(NH3)Cl5]. Die Kristallchemie der Salze (NH4)2[V(NH3)Cl5], [Rh(NH3)5Cl]Cl2 und M2VXCl5 mit M = K,NH4, Rb,Cs und X = Cl,O

Preparation and Crystal Structure of (NH₄)₂[V(NH₃)Cl₅]. The Crystal Chemistry of the Compounds (NH₄)₂[V(NH₃)Cl₅], [Rh(NH₃)₅Cl]Cl₂, and M₂VXCl₅ with M = K, NH₄, Rb, Cs and X ? Cl, O (NH₄)₂[V(NH₃)Cl₅] crystallizes like [Rh(NH₃)₅Cl]Cl₂ in the orthorhombic space group Pnma with Z = 4. The compounds are built up by isolated NH₄⁺ or Cl^? and complex MX₅Y ions. The following distances have been observed: V? N: 213.8, V? Cl: 235.8–239.1, Rh? N: 207.1–208.5, Rh? Cl: 235.5 pm. Both structures differ from the K₂PtCl₆ type mainly in the ordering of the MX₅Y polyhedra. The compounds M₂VCl₆ and M₂VOCl₅ with M = K, NH₄, Rb, and Cs crystallize with exception of the orthorhombic K₂VOCl₅ in the K₂PtCl₆ type. The ordering of the MX₅Y polyhedra in the compounds (NH₄)₂[V(NH₃)Cl₅], [Rh(NH₃)₅Cl]Cl₂ and K₂VOCl₅ enables a closer packing.     

Darstellung und Kristallstruktur von Tetraphenylphosphonium-Hexathiocyanatorhodat(III), [P(C6H5)4]3[Rh(SCN)6]

Preparation and Crystal Structure of Tetraphenylphosphonium Hexathiocyanatorhodate(III), [P(C₆H₅)₄]₃[Rh(SCN)₆] By treatment of RhCl₃ · n H₂O with KSCN in water a mixture of the linkage isomers [Rh(NCS)_n(SCN)_6–n]^3?, n = 0–2 is formed which is separated by ion exchange chromatography on diethylaminoethyl cellulose. The X-ray structure determination on a single crystal of [P(C₆H₅)₄]₃[Rh(SCN)₆] (monoclinic, space group C1c1, a = 13.620(5), b = 22.929(13), c = 22.899(9) Å, β = 98.55(3)°, Z = 4) confirms the coordination of all ligands via S with the middle Rh? S distance of 2.372 Å and Rh? S? C angles of 109°. The SCN groups are nearly linear with 175° and averaged bondlengths S? C 1.63 and C? N 1.14 Å. The crystal lattice is build up by layers of complex anions and voluminous cations with no specific interactions but which are closely connected by thiocyanate ligands and phenyl rings.     

Amidometallate von Lanthan und Gadolinium und Umsetzung von Lanthan,Gadolinium und Scandium mit Ammoniak

Amidometallates of Lanthanum and Gadolinium and the Conversion of Lanthanum, Gadolinium, and Scandium with Ammonia By reaction of the metals with NsNH₂ and NH₃ in the hightemperature- autoclave Na₃[La(NH₂)₆], Na₃[Gd(NH₂)₆], and Na[Gd(NH₂)₄] were prepared, but not any compound of Sc. By corresponding experiments with NH₄I only La(NH₂)₃, GdN, and ScH₂ were obtained. Na₃[La(NH₂)₆] and Na₃[Gd(NH₂)₆] are isotypic with Na₃[Y(KH₂)₆], Na[Gd(NH₂)₄] with Na[Yb((NH₂)₄]. The thermal behaviour of the prepared amides was characterized by DTA and tensimetry.     

Über die Ammonolyse von Organometallen. XI. Die Ammonolyse von Diphenylbleijodid, — Bildung von Kaliumhexaamidoplumbat (IV)

The reaction of (C₆H₅)₂PbJ₂ (I) in liquid NH₃ with KNH₂ has been investigated. It results in the formation of K₂[Pb(NH₂)₆] (II). As intermediates could be isolated: (C₆H₅)₂PbJ₂ · 3NH₃ (III), (C₆H₅)₂PbNH (V) and K₂[(C₆H₅)₂Pb(NH₂)₄] (VIII).     

Darstellung,Redox-Verhalten und Strukturen einkerniger „einfacher”︁ Mono- und Dinitrosyl-Komplexe des Molybdäns mit Hydroxylamido(−1)-, Oximato-, Halogeno- und Pseudohalogeno-Liganden

Preparation, Redox Properties, and Structures of Mononuclear ?Simple”? Mono-, and Dinitrosyl Complexes of Molybdenum with Hydroxylamido(?1), Oximato, Halogeno, and Pseudohalogeno Ligands The compounds [(C₆H₅)₄P]₂[Mo(NO)(H₂NO)(NCS)₄] 1 , [(C₆H₅)₄P]₂ [Mo(NO)((C₂H₅)₂-CNO)(NCS)₄] 2 , [(C₆H₅)₄P]₂[Mo(NO)₂(NCS)₄] · CH₃OH, 3 [(C₆H₅)₄P]₃[Mo(NO)(CN)₅] · 2H₂O 4 , Cs₂[Mo(NO)Cl₄(H₂O)] 5 and Cs₂[Mo(NO)Cl₅] 6 were prepared and characterized by complete X-ray structure analysis. All complexes have a nearly linear MoNO moiety, whereas in the anions of 1 and 2 a pentagonal-bipyramidal, in 3 — 6 an octahedral coordination sphere of Mo is present. Complexes with {MoNO}ⁿ configuration (n = 4, 5, 6) can be converted into each other by remarkable redox-reactions. Some novel reactions of the hydroxylamido(?1)-ligand (formation of 2 and 3 ) are discussed very shortly.     

Über Cyanatverbindungen und deren reaktives Verhalten. XXI. Reaktionsverhalten von Niob(V)- und Tantal(V)-thiocyanat gegenüber N-Donatoren

Cyanate Compounds and their Reactivity. XXI. Reactivity of Niobium(V) and Tantalum(V) Thiocyanates to N-Donators M₂(NCS)₁₀ reacts with ammonia or primary and secondary aliphatic amines to complexes of the types [M(NCS)(NH₂)₂NH]_x, [M(NCS)₃(NHR)₂ H₂NR], or [M(NCS)₃(NR′₂)₂ HNR′₂], with N-heterocyclic amines in a first step to [M(NCS)₅L]-complexes and in a further step through a redox mechanism to [M(NCS)₄L₂] complexes. [M(NCS)₅(CH₃CN)] mCH₃CN reacts with ammonia, or primary amines in acetonitrile over acetamidine and amidinolytic cleavage of M-NCS bonds to complexes of the type [M(NCS)_a(NC(NHR″)CH₃)_b(CH₃C(NH)NHR″)]_x. The prepared compounds are characterized by analytical data, derivatographic measurements, and IR or visible absorption spectra (M = Nb, Ta; x = 2; R = n-C₄H₉; R′ = C₂H₅; L = pyridine or 4-methyl-pyridine; m = 0, 1, 2; a = 1 or 4; b = 4 or 1; R″ = H, n-C₄H₉).     

Darstellung und Kristallstruktur von (n-Bu4N)3[Ir(NCS)(SCN)5]

Preparation and Crystal Structure of (n-Bu₄N)₃[Ir(NCS)(SCN)₅] The evaporated ethanolic extrakt of the reaction product of K₃[IrCl₆] and HNO₃, refluxed with an aqueous KSCN solution yields a mixture of the linkage isomers [Ir(NCS)_n(SCN)_6?-n]^3?, n = 0? 2, and small amounts of linkage isomeric chloropentarhodanoiridates(III), from which [Ir(NCS)(SCN)₅]^3? has been isolated by ion exchange chromatography on DEAE-cellulose. The X-Ray structure determination on a single crystal of (n-Bu₄N)₃[Ir(NCS)(SCN)₅] (monoclinic, space group P 2₁/a, a = 17.513(5), b = 32.607(5), c = 23.661(5) Å, β = 94.757(5)°, Z = 8) confirms the existance of a heteroleptic hexakis(thiocyanato(N)-thiocyanato(S))iridate(III) with an Ir? N distance of 2.03 Å and Ir? S bond lengths between 2.29 and 2.38 Å. The SCN groups with angles between 166 and 175° are nearly linear with Ir? S? C angles from 99.9 to 109.4°. The Ir? N? C angles of the two crystallographic independent anions are 166 and 174°.     

Complex Carbonates of Iron(III)

The complex carbonates of iron(III) are shown to be anionic in nature. The solutions containing these complexes show a maximum absorbance at 460 nm. The complex carbonates of iron(III), viz., (i) K₆[Fe₂(OH)₂(CO₃)₅] · H₂O, — (ii) Na₂[Fe₃O₂(OH)₃(CO₃)₂], — (iii) K[Co(NH₃)₆]₂[Fe₃(OH)₄(CO₃)₆], — (iv) K₅[Co(NH₃)₆]₃[Fe₃(OH) ₄(CO₃)₆]₂, — (v) K[Co(NH₃)₆][Fe₂(OH)₄(CO₃)₃], and (vi) NH₄[Co(NH₃)₆][Fe₂(OH)₄(CO₃)₃] are isolated and studied by thermogravimetry. The infrared spectra of these compounds are recorded and probable band assignments made. Besides, the reaction between KHCO₃ and Fe(NO₃)₃ was studied through chemical and physicochemical methods.     

Darstellung und Eigenschaften der Alkali-hexajodatogermanate (IV), M2[Ge(JO3)6]

Preparation and Properties of the Alkali Hexaiodatogermanates(IV), M₂[Ge(IO₃)₆] Germanium dioxide aquate and alkali nitrates react with iodic acid to yield alkali hexaiodatogermanates(IV), M₂[Ge(IO₃)₆], (M = NH₄, K, Rb, Cs). The unit-cell dimensions of the trigonal cell are for K₂[Ge(JO₃)₆] a₀ = 11.16 Å, c₀ = 11.34 Å, z = 3. The compounds M[M^IV(IO₃)₆] (M^I = NH₄, K, Rb, Cs, M^IV = Ge, Sn, Pb, Ti, Zr, Mn) are isomorphous¹).     

Zur Kenntnis der Sulfito-kobalt(III)-Ammine. II. [CoSO3NCS(NH3)4] und [CoSO3SCN(NH3)4]

Sulphito Cobalt(III) Ammines. II. [CoSO₃NCS(NH₃)₄] and [CoSO₃SCN(NH₃)₄] The brown complex [CoSO₃NCS(NH₃)₄] · 2 H₂O formed from aqueous solutions contains N-bonded thiocyanate as concluded from his IR spectrum. After dehydration the red complex [CoSO₃SCN(NH₃)₄] containing S-bonded thiocyanate has been formed. The conversion of the two isomers is favoured by the trans effect of the sulphito group.     

Synthese und Struktur von Ammin- und Amidokomplexen des Iridiums

Synthesis and Structure of Ammine and Amido Complexes of Iridium The reaction of (NH₄)₂[IrCl₆] with NH₄Cl at 300 °C in a sealed glass ampoule yields the iridium(III) ammine complex (NH₄)₂[Ir(NH₃)Cl₅], which crystallizes isotypically with K₂[Ir(NH₃)Cl₅] in the orthorhombic space group Pnma with Z = 4, and a = 1350.0(2); b = 1028.5(3); c = 689.6(2) pm. The reaction of (NH₄)₂[IrCl₆] with NH₃ at 300 °C, however, gives the already known [Ir(NH₃)₅Cl]Cl₂ beside a small amount of [Ir(NH₃)₄Cl₂]Cl₂. In pure form [Ir(NH₃)₅Cl]Cl₂ is obtained by ammonolysis of (NH₄)₂[Ir(NH₃)Cl₅] at 300 °C with NH₃. [Ir(NH₃)₄Cl₂]Cl₂ crystallizes triclinic (P1, Z = 1, a = 660,2(3); b = 680,4(3); c = 711,1(2) pm; α = 103,85(2)°, β = 114,54(3)°, γ = 112,75(2)°). The structure contains Cl^– anions and [Ir(NH₃)₄Cl₂]²⁺ cations with a trans position of the Cl atoms. Upon reaction of [Ir(NH₃)₅Cl]Cl₂ with Cl₂ one ammine ligand is eliminated yielding [Ir(NH₃)₄Cl₂]Cl, which is transformed to orthorhombic [Ir(NH₃)₄(OH₂)Cl]Cl₂ (Pnma, Z = 4, a = 1335,1(3); b = 1047,9(2); c = 673,4(2) pm) by crystallization from water. In the octahedral complex [Ir(NH₃)₄(OH₂)Cl]²⁺ the four ammine ligands have an equatorial position, whereas the Cl atom and the aqua ligand are arranged axial. Oxidation of (NH₄)₂[Ir(NH₃)Cl₅] with Cl₂ at 330 °C affords the tetragonal Ir^IV complex (NH₄)[Ir(NH₃)Cl₅] (P4nc, Z = 2, a = 702.68(5); c = 912.89(9) pm). Its structure was determined using the powder diagram. Oxidation of (NH₄)₂[Ir(NH₃)Cl₅] with Br₂ in water, on the other hand, gives (NH₄)₂[IrBr₆] crystallizing in the K₂[PtCl₆] type. Oxidation of (PPh₄)₂[Ir(NH₃)Cl₅] with PhI(OAc)₂ in CH₂Cl₂ affords the Ir^V amido complex (PPh₄)[Ir(NH₂)Cl₅].     

Rubidiumhexaamidolanthanat und -neodymat,Rb3[La(NH2)6] und Rb3[Nd(NH2)6]; Strukturverwandtschaft zu K3[Cr(OH6)] und K4CdCl6

Rubidium Hexaamidolanthanate and -neodymate, Rb₃[La(NH₂)₆] and Rb₃[Nd(NH₂)₆]; Compounds. Structurally Related to K₃[Cr(OH)₆] and K₄CdCl₆ Colourless Rb₃[La(NH₂)₆] (a = 12.298(4) Å, c = 13.759(2) Å, N = 6, R3 c) and pale blue Rb₃[Nd(NH₂)₆] (a = 12.199(6) Å, c = 13.626(4) Å, N = 6, R32) have been prepared by the reaction of the corresponding metals (Rb: La resp. Nd = 3:1) with NH₃(P(NH₃) = 4–4.5 kbar) at 300°C. Single crystal x-ray methods gave their structures. It is shown by space group relations that these compounds are structurally related to one another and to further ternary amides as well as to K₃[Cr(OH)₆] and K₄CdCl₆.     

[(C6H5)4P]2[Mo(NO)(ONC(CH3)2)(NCS)4], ein Komplex mit einem side-on gebundenen Oximato-Liganden; Kristall- und Molekülstruktur

[(C₆H₅)₄P]₂[Mo(NO)(ONC(CH₃)₂)(NCS)₄], a Complex Having a Side-on Coordinated Oximato Ligand; Crystal and Molecular Structure The structure of the title compound 1 was determined from single-crystal X-ray data 1 crystallizes in the triclinic space group P1 . Mo has a pentagonal-bipyramidal coordination sphere. The oximato-ligand is side-on bonded in the equatorial plane. (Mo? N and Mo? O bond lengths: 2.086(8) and 2.090(6) Å, respectively) (R = 0.082; R_w = 0,077).     

Kristallstrukturen,Schwingungsspektren und Normalkoordinatenanalyse von (n‐Bu4N)2[Os(NCS)6] und (n‐Bu4N)3[Os(NCS)6]

Crystal Structure, Vibrational Spectra, and Normal Coordinate Analysis of ( n ‐Bu₄N)₂[Os(NCS)₆] and ( n ‐Bu₄N)₃[Os(NCS)₆] By tempering the solid mixture of the linkage isomers (n‐Bu₄N)₃[Os(NCS)_n(SCN)_6–n] n = 0–5 for a longer time at temperatures increasing from 60 to 140 °C the homoleptic (n‐Bu₄N)₃[Os(NCS)₆] is formed, which on oxidation with (NH₄)₂[Ce(NO₃)₆] in acetone yields the corresponding Os^IV complex (n‐Bu₄N)₂[Os(NCS)₆]. X‐ray structure determinations on single crystals of (n‐Bu₄N)₂[Os(NCS)₆] (1) (triclinic, space group P 1, a = 12.596(5), b = 12.666(5), c = 16.026(5) Å, α = 88.063(5), β = 80.439(5), γ = 88.637(5)°, Z = 2) and (n‐Bu₄N)₃[Os(NCS)₆] ( 2 ) (cubic, space group Pa 3, a = 24.349(4) Å, Z = 8) have been performed. The nearly linear thiocyanate groups are coordinated with Os–N–C angles of 172.3–177.7°. Based on the molecular parameters of the X‐ray determinations the IR and Raman spectra are assigned by normal coordinate analysis. The valence force constant f_d(OsN) is 2.3 ( 1 ) and 2.10 mdyn/Å ( 2 ).     

Kristallstruktur von Tetraphenylphosphonium-Monothiocyanatohydro-closo-Decaborat, [P(C6H5)4]2[2-(SCN)B10H9] · CH3CN

Crystal Structure of Tetraphenylphosphonium Monothiocyanatohydro-closo-Decaborate, [P(C₆H₅)₄]₂[2-(SCN)B₁₀H₉] · CH₃CN The X-ray structure determination of [P(C₆H₅)₄]₂[2-(SCN)B₁₀H₉] · CH₃CN (monoclinic, space group P2₁/n, a = 10.6040(10), b = 13.8880(9), c = 33.888(3) Å, β = 94.095(8)°, Z = 4) reveals the S coordination of the SCN substituent with a B? S distance of 1.913(6) Å and a B? S? C angle of 105.3(3)°. The SCN group is nearly linear (178.2(7)°).     

Synthesis and characterisation of [tris(1,3-dithiole-2-thione-4,5-dithiolato)-stannate]2−, [Q]2[Sn(dmit)3], [tris(1,3-dithiole-2-one-4,5-dithiolato)stannate]2−, [Q]2[Sn(dmio)3] and [tris(1,3-dithiole-2-thione-4,5-selenolato)stannate]2−, [Q]2[Sn(dsit)3], complexes: Analysis of the structural variations of the [Sn(dmit)3]2− and [Sn(dmio)3]2− dianions

[Tris(1,3-dithiole-2-thione-4,5-dithiolato)stannate]²⁻, [Q]₂[Sn(C₃S₅)₃], [tris(1,3-dithiole-2-one-4,5-dithiolato)stannate]²⁻, [Q]₂[Sn(C₃S₄O)₃], and [tris(1,3-dithiole-2-thione-4,5-diselenolato)stannate]²⁻ [Q]₂[Sn(C₃S₃Se₂)₃], complexes, have been synthesised and characterised. Crystal structure determinations of [Q]₂[Sn(C₃S₅)₃] (Q=1,4-dimethylpyridinium, monoclinic and orthorhombic forms; NMe₄, NEt₄, and PPh₄) and [NEt₄]₂[Sn(C₃S₄O)₃] revealed variations in the overall dianion structures. The geometry about tin in each case is essentially octahedral with the chelate bite angles in the range 80.7(5)–87.45(4)°: the range of Sn–S distances is 2.5207(18)–2.571(17) Å. A statistical analysis, carried out on the crystal structure data for the six complexes, indicated that the most critical factors in controlling the overall shape of the dianion were the distances of the Sn atom from the dithiolate ligand planes [Sn–OOP]. Interanionic S⋯S interactions, within the sum of the van der Waals’ radii for two S atoms, are affected by the size of the cation, Q; the secondary connectivity is 3-dimensional for the smallest cations, Q=1,4-dimethylpyridinium and NMe₄, in chains for the somewhat larger cation, NEt₄ and is absent for the still larger, PPh₄ cation.