Ternäre Alkalimetall‐Übergangsmetall‐Acetylide der Zusammensetzung A2MC2 mit A = Rb,Cs und M = Pd,Pt

Ternary Alkali Metal Transition Metal Acetylides A₂MC₂ with A = Rb, Cs, and M = Pd, Pt By the reaction of Rb₂C₂ and Cs₂C₂ with palladium or platinum powder in sealed glass ampoules at 653 K ternary acetylides A₂MC₂ (A = Rb, Cs; M = Pd, Pt) were obtained. Their crystal structures were solved and refined by means of X‐ray powder investigations (Na₂PdC₂ structure type, P 3 m1, Z = 1). The crystal structures are characterised by [M(C₂)_2/2^2–] chains separated by the alkali metals. Raman spectroscopic investigations revealed wave numbers of the C–C stretching vibrations between 1833 and 1842 cm^–1, which are in good agreement with the results of the analogous sodium and potassium compounds.     

Kristallstrukturen und thermisches Verhalten von Metalldihydrogenphosphat‐HF‐Addukten MH2PO4 · HF (M = K,Rb, Cs) mit Wasserstoffbrückenbindungen vom Typ F–H…O

Structures and Thermal Behaviour of Alkali Metal Dihydrogen Phosphate HF Adducts, MH₂PO₄ · HF (M = K, Rb, Cs), with Hydrogen Bonds of the F–H…O Type Three HF adducts of alkali metal dihydrogen phosphates, MH₂PO₄ · HF (M = K, Rb, Cs), have been isolated from fluoroacidic solutions of MH₂PO₄. KH₂PO₄ · HF crystallizes monoclinic: P2₁/c, a = 6,459(2), b = 7,572(2), c = 9,457(3) Å, β = 101,35(3)°, V = 453,5(3) ų, Z = 4. RbH₂PO₄ · HF and CsH₂PO₄ · HF are orthorhombic: Pna2₁, a = 9,055(3), b = 4,635(2), c = 11,908(4) Å, V = 499,8(3) ų, Z = 4, and Pbca, a = 7,859(3), b = 9,519(4), c = 14,744(5) Å, V = 1102,5(7) ų, Z = 8, respectively. The crystal structures of MH₂PO₄ · HF contain M⁺ cations, H₂PO₄^– anions and neutral HF molecules. The H₂PO₄^– anions are connected to layers by O–H…O hydrogen bonds (2,53–2,63 Å), whereas the HF molecules are attached to the layers via very short hydrogen bonds of the F‐H…O type (2,36–2,38 Å). The thermal decomposition of the adducts proceeds in three steps. The first step corresponds to the release of mainly HF and a smaller quantity of water. In the second and third steps, water evolution caused by condensation of dihydrogen phosphate is the dominating process whereas smaller amounts of HF are also released.     

Kristallstrukturen,spektroskopische Charakterisierung und Normalkoordinatenanalyse von (n‐Bu4N)2[M(ECN)4] (M = Pd,Pt; E = S,Se)

Crystal Structures, Spectroscopic Analysis, and Normal Coordinate Analysis of ( n ‐Bu₄N)₂[M(ECN)₄] (M = Pd, Pt; E = S, Se) The reaction of (NH₄)₂[PdCl₄] or K₂[PtCl₄] with KSCN or KSeCN in aqueous solutions yields the complex anions [Pd(SCN)₄]^2–, [Pt(SCN)₄]^2– and [Pt(SeCN)₄]^2–, which are converted into (n‐Bu₄N) salts with (n‐Bu₄N)HSO₄. (n‐Bu₄N)₂[Pd(SeCN)₄] is formed by treatment of (n‐Bu₄N)₂[PdCl₄] with (n‐Bu₄N)SeCN in acetone. X‐ray structure determinations on single crystals of (n‐Bu₄N)₂[Pd(SCN)₄] (monoclinic, space group P2₁/n, a = 13.088(3), b = 12.481(2), c = 13.574(3) Å, β = 91.494(15)°, Z = 2), (n‐Bu₄N)₂[Pd(SeCN)₄] (monoclinic, space group P2₁/n, a = 13.171(2), b = 12.644(2), c = 13.560(2) Å, β = 91.430(11)°, Z = 2) and (n‐Bu₄N)₂[Pt(SeCN)₄] (monoclinic, space group P2₁/n, a = 13.167(2), b = 12.641(1), c = 13.563(2) Å, β = 91.516(18)°, Z = 2) reveal, that the compounds crystallize isotypically and the complex anions are centrosymmetric and approximate planar. In the Raman spectra the metal ligand stretching modes of (n‐Bu₄N)₂[Pd(SCN)₄] ( 1 ) and (n‐Bu₄N)₂[Pt(SCN)₄] ( 3 ) are observed in the range of 260–303 cm^–1 and of (n‐Bu₄N)₂[Pd(SeCN)₄] ( 2 ) and (n‐Bu₄N)₂[Pt(SeCN)₄] ( 4 ) in the range of 171–195 cm^–1. The IR and Raman spectra are assigned by normal coordinate analysis using the molecular parameters of the X‐ray determination. The valence force constants are f_d(PdS) = 1.17, f_d(PdSe) = 1.17, f_d(PtS) = 1.44 and f_d(PtSe) = 1.42 mdyn/Å. The ⁷⁷Se NMR resonances are 23 for 2 , –3 for 4 and the ¹⁹⁵Pt NMR resonances 549 for 3 and 130 ppm for 4 .     

Syntheses and Crystal Structures of Novel Ternary Alkali Metal Gold Acetylides MIAuC2 (MI = Li,Na, K,Rb, Cs)

By the reaction of AuI with alkali metal hydrogen acetylides M^IC₂H (M^I = Li–Cs) in liquid ammonia and subsequent heating of the remaining residue in refluxing pyridine (M^I = Li, Na, K) or as a solid phase at about 110 °C in vacuum (M^I = Rb, Cs) ternary alkali metal gold acetylides M^IAuC₂ were obtained. Their crystal structures were investigated by the means of X‐ray powder diffraction. [Au(C₂)_2/2^–] chains are the characteristic structural motif which are packed in a hexagonal (LiAgC₂) and tetragonal arrangement (NaAuC₂–CsAuC₂), respectively. Simple calculations based on the close packing of rods and spheres can explain these different arrangements. The existence of C–C triple bonds in the title compounds is confirmed by Raman spectroscopic investigations.     

Synthese,Struktur und Eigenschaften von [nacnac]MX3‐Verbindungen (M = Ge,Sn; X = Cl,Br, I)

Synthesis, Structure, and Properties of [nacnac]MX₃ Compounds (M = Ge, Sn; X = Cl, Br, I) Reactions of [nacnac]Li [(2,6‐ⁱPr₂C₆H₃)NC(Me)C(H)C(Me)N(2,6‐ⁱPr₂C₆H₃)]Li ( 1 ) with SnX₄ (X = Cl, Br, I) and GeCl₄ in Et₂O resulted in metallacyclic compounds with different structural moieties. In the [nacnac]SnX₃ compounds (X = Cl 2 , Br 3 , I 4 ) the tin atom is five coordinated and part of a six‐membered ring. The Sn–N‐bond length of 3 is 2.163(4) Å and 2.176(5) Å of 4 . The five coordinated germanium of the [nacnac]GeCl₃ compound 5 shows in addition to the three chlorine atoms further bonds to a carbon and to a nitrogen atom. In contrast to the known compounds with the [nacnac] ligand the afore mentioned reaction creates a carbon–metal‐bond (1.971(3) Å) forming a four‐membered ring. The Ge–N bond length (2.419(2) Å) indicates the formation of a weakly coordinating bond.     

Synthesis of Li2PtH6 using high pressure: Completion of the homologous series A2PtH6 (A=alkali metal)

Li₂PtH₆, the missing member of the complex transition metal hydride series A₂PtH₆ (A=alkali metal), was prepared by reacting mixtures of LiH and Pt in the presence of BH₃NH₃ as hydrogen source at pressures above 8 GPa. According to powder X-ray diffraction analysis, Li₂PtH₆ is isostructural to its heavier homologues and crystallizes in the cubic K₂PtCl₆ structure (space group Fm3¯m, a=6.7681(3), Z=4). However, PtH₆²⁻ octahedral complexes in Li₂PtH₆ approach each other closely and its structure may likewise be regarded as a defective perovskite structure where half of the octahedrally coordinated atoms (cations) are missing. The IR spectrum of Li₂PtH₆ reveals the Pt-H T_1u stretch and bend at 1840 and 889 cm⁻¹, respectively.     

{Ph2(Carb)P}MCl3 (M = Pd,Pt; Carb = 2,3-dihydro-1,3-diisopropyl-4,5dimethylimidazol-2-ylidene) – a Novel Cationic Phosphane Ligand [1]

The phosphane ligand [Ph₂(Carb)P]⁺ forms neutral complexes {Ph₂(Carb)P}MCl₃ (Carb = 2,3-dihydro-1,3-diisopropyl-4,5-dimethylimidazol-2-ylidene; M = Pd, Pt) through the reaction of it's chloride salt with (PhCN)₂MCl₂; the triarylphosphane type properties of the ligand are revealed by n.m.r. and structural data.     

Synthese und Metallierungen der tripodalen Siloxazan-Liganden tBuSi(OSiMe2NHR)3 [R = H,Me, tBu,Ph, SiMe3]

Synthesis and Metalation of Tripodal Siloxazane Ligands ^tBuSi(OSiMe₂NHR)₃ [R = H, Me, ^tBu, Ph, SiMe₃] ^tBuSi(OSiMe₂Cl)₃ ( 1 ) was generated by the condensation of tert-butylsilanetriol with dichlorodimethylsilane under elimination of HCl. A series of tripodal amines ^tBuSi(OSiMe₂NHR)₃ [R = H ( 2 ), R = Me ( 3 ), R = ^tBu ( 4 ), R = Ph ( 5 )] was synthesized by ammonolysis, aminolysis or salt elimination of 1 with primary lithium amides. 5  has been subjected to single crystal X-ray diffraction, which confirmed the triarmed amine. The siloxamine ^tBuSi(OSiMe₂NHSiMe₃)₃ ( 6 ) was generated by the reaction of 2 with three moles of chlorotrimethylsilane. The lithium amides ^tBuSi(OSiMe₂N[Li]^tBu)₃ ( 7 ), ^tBuSi(OSiMe₂N[Li]Ph)₃ ( 8 ) and ^tBuSi(OSiMe₂N[Li]SiMe₃)₃ ( 11 ) and the sodium amide ^tBuSi(OSiMe₂N[Na]^tBu)₃ ( 9 ) were obtained by the complete hydrogen–metal exchange of the amines 4 – 6 with n-butyl lithium and n-butyl sodium in hexane, respectively. The transmetalation of 7 with copper(I) chloride gave the copper amide ^tBuSi(OSiMe₂N[Cu]^tBu)₃ ( 10 ). The single crystal X-ray diffraction of the metal amides 7 , 9 and 11 shows a trifold coordination by additional interactions between each of the two metal atoms with oxygens in the siloxane groups in contrast to the copper amide 10 , which lacks such contacts. The almost isostructural metal amides 7 , 9 – 11 are monomeric and possess, similary to 5 , a pseudo three fold symmetry in the solid state. 5 and 7 crystallize in the monoclinic space group P2₁/c whereas the compounds 9 – 11 crystallize in the centrosymmetric triclinic space group P 1.     

Reaktionen von Trimethylstiban in den supersauren Systemen XF/MF5 (X = H,D; M = As,Sb), Kristallstrukturen von (CH3)3SbD+SbF6– und (CH3)3SbSb(CH3)32+(SbF6–)2 · SO2

Reactions of Trimethylstibine in the Superacidic Systems XF/MF₅ (X = H, D; M = As, Sb), Crystal Structures of (CH₃)₃SbD⁺SbF₆^– and (CH₃)₃SbSb(CH₃)₃²⁺(SbF₆^–)₂ · SO₂ The reaction of trimethylstibine in the superacidic systems XF/MF₅ (M = As, Sb; X = H, D) leads to the trimethylstibonium hexafluorometallates. The resulting salts are characterised by vibrational spectroscopy and their crystal structures. Decomposition of trimethylstibonium hexafluoroantimonate in sulphur dioxide at room temperature ends in the formation of hexamethyldistibonium bis(hexafluoroantimonate) as a sulphur dioxide adduct, verified by its crystal structure and vibrational spectra.     

The Evolution Aspect in the Crystallization Process of [5,5′‐(HCF2CF2CH2OCH2)2‐2,2′‐bpy]MX2 (M = Pt,Pd; X = I,Br): Role of the Intramolecular CF2─H…X(─M) Hydrogen Bonds

The general species (2,2′‐bpy)MX₂ (M = Pd, Pt; X = Br, I) in a crystallization process results in an isomorphous convergence in P2₁/c. Yet, with polyfluorinated side chains, the general [5,5′‐(HCF₂CF₂CH₂OCH₂)₂‐2,2′‐bpy]MX₂ species proceeds to crystallize the isomorphous structures of 5 (M = Pt; X = I) and 6 (M = Pd; X = I) in P2₁/c only; structure 7 (M = Pt; X = Br) crystallizes in P2₁/c but is not isomorphous with 5 and 6 , and structure 8 (M = Pd; X = Br) forms differently in P–1. The causes making the system nonlinear are (1) the intramolecular CF₂─H^…X(─M) hydrogen bonds found in 5–7 but not in 8, and (2) in response to the transition from I to Br, bifurcated [C─H^…]₂ F ─C hydrogen bonds that are formed in 5 and 6 and bifurcated C─ H [^…F─C]₂ hydrogen bonds in 7 . Additionally, the intramolecular CF₂─H^…X(─M) hydrogen bonding from compounds 5–7 could be affirmed by the IR studies.     

Darstellung und spektroskopische Charakterisierung der Difluoramino-fluoriminium-Hexafluorometallate F2NC(F)NX2+MF6– (X = H,D; M = As,Sb)

Preparation and Spectroscopic Characterization of the Difluoroaminofluoro-iminium-hexafluorometallates F₂NC(F)NX₂⁺MF₆^– (X = H, D; M = As, Sb) Difluorocyanamin, F₂NCN, does not react with the superacids XF/MF₅ (X = H, D; M = As, Sb) under formation of protonated nitrilium salts. At –78 °C iminium salts of the general form F₂NC(F)NX₂⁺MF₆^– are observed, which are characterized by vibrational and nmr spectroscopy. The structure and vibrational frequencies were computed ab initio at the Hartree-Fock (HF/6-31 + G*) and correlated Møller-Plesset (MP2/6-31 + G*) levels of theory.     

Platinum(II) and Palladium(II) Bis(chelate) Complexes Containing both Tri(1‐cyclohepta‐2, 4, 6‐trienyl)phosphane,P(C7H7)3, and Dichalcogenolato Ligands

Tri(1‐cyclohepta‐2, 4, 6‐trienyl)phosphane, P(C₇H₇)₃ ([P] when coordinated to a metal atom), was used to stabilize complexes of platinum(II) and palladium(II) with chelating dichalcogenolato ligands as [P]M(E∩E) [E = S, ∩ = CH₂CH₂, M = Pt ( 3a ); E = S, ∩ = 1, 2‐C₆H₄, M = Pt ( 5a ), Pd ( 6a ); E = S, ∩ = C(O)C(O), M = Pt ( 7a ), Pd ( 8a ); E = S, Se, ∩ = 1, 2‐C₂(B₁₀H₁₀), M = Pt ( 9a, 9b ), Pd ( 10a, 10b ); E = S, ∩ = Fe₂(CO)₆, M = Pt ( 11a ), Pd ( 12a )]. Starting materials in all reactions were [P]MCl₂ with M = Pt ( 1 ) and Pd ( 2 ). Attempts at the synthesis of [P]M(ER)₂ with non‐chelating chalcogenolato ligands were not successful. All new complexes were characterized by multinuclear magnetic resonance spectroscopy in solution (¹H, ¹³C, ³¹P, ⁷⁷Se and ¹⁹⁵Pt NMR), and the molecular structures of 5a and 12a were determined by X‐ray analysis. Both in the solid state and in solution the ligand [P] is linked to the metal atom by the P‐M bond and by η²‐C=C coordination of the central C=C bond of one of the C₇H₇ rings. In solution, intramolecular exchange between coordinated and non‐coordinated C₇H₇ rings is observed, the exchange process being markedly faster in the case of M = Pd than for M = Pt.     

Synthesis and Structures of Bis(alkene) Complexes of Tungsten and Molybdenum, [M(CO)2(dpphen)(dbf)2] (M = W or Mo; dpphen = 4,7‐diphenyl‐1,10‐phenanthroline; dbf = dibutylfumarate)

Tungsten and molybdenum complexes [M(CO)₂(dpphen)(dbf)₂] (M = W 1 or Mo 2 ; dpphen = 4,7‐diphenyl‐1,10‐phenanthroline; dbf = dibutylfumarate) have been synthesized and structurally characterized by X‐ray diffraction analysis. In both complexes which have similar structure, the metal atom co‐ordination is distorted octahedral with dpphen and two CO groups in the equatorial plane and the metal atom binds in an η²‐fashion to the C–C bonds of two dbf ligands. The two C–C bonds are almost mutually orthogonal. The two complexes are different in conformation which result from face selection of the two dbf ligands for coordination to the metal atom.     

Kristallstrukturbestimmungen an Cs2NaCr(CN)6 und weiteren Verbindungen A2BM(CN)6 (A = Rb,Cs; B = Na,K, Rb,NH4; M = Cr,Mn, Fe,Co): Oktaederkippung und Toleranzfaktor von Cyanokryolithen

Crystal Structure Determinations of Cs₂NaCr(CN)₆ and further Compounds A₂BM(CN)₆ (A = Rb, Cs; B = Na, K, Rb, NH₄; M = Cr, Mn, Fe, Co): Tilting of Octahedra and Tolerance Factor of Cyano Cryolites The crystal structures of Cs₂NaCr(CN)₆ (space group P2₁/n, Z = 2; a = 763.2(1), b = 789.8(1), c = 1102.4(1) pm, β = 90.09(1)°) and of 9 isostructural cyano cryolites A₂BM(CN)₆ of the elements M = Cr, Mn, Fe, Co were determined by X‐rays at single crystals. The results, including data from the literature, were studied with respect to the interdependence of radii resp. bond lengths and cyano bridge angles M–CN–B resp. tilting of [M(CN)₆] and [BN₆] octahedra: The average tilt angles κ of the latter are within the range 13° ≤ κ ≤ 23° and increase linearly if the modified tolerance factor t (of range 0,87 ≥ t ≥ 0,78) decreases.     

IR- und Raman-Spektren der isotypen Iodathydrate M(IO3)2 · 4 H2O (M = Mg,Ni, Co); Kristallstruktur von Co(IO3)2 · 4 H2O

Infrared and Raman Spectroscopy of the Isostructural Iodate Hydrates M(IO₃)₂ · 4 H₂O (M = Mg, Ni, Co)-Crystal Structure of Cobalt Iodate Tetrahydrate The iodate tetrahydrates Mg(IO₃)₂ · 4 H₂O, β-Ni(IO₃)₂ · 4 H₂O, Co(IO₃)₂ · 4 H₂O and their deuterated specimens were studied by X-ray, infrared and Raman spectroscopic methods. The title compounds are isostructural crystallising in the monoclinic space group P2₁/c (Z = 2). The crystal structure of Co(IO₃)₂ · 4 H₂O (a = 836.8(5), b = 656.2(3), c = 850.2(5) pm and β = 100.12(5)°) has been refined by single-crystal X-ray methods (R_obs = 3.08%, 693 unique reflections I₀ > 2σ(I)). Isolated Co(IO₃)₂(H₂O)₄ octahedra form layers parallel (100). Within these layers, the two crystallographically different hydrate water molecules form nearly linear hydrogen bonds to adjacent IO₃^– ions (ν_OD of matrix isolated HDO of Co(IO₃)₂ · 4 H₂O (isotopically diluted samples) 2443 (H3), 2430 (H2), and 2379 cm^–1 (H1 and H4), –180 °C). Intramolecular O–H and intermolecular H…O distances were derived from the novel ν_OD vs. r_OH and the traditional ν_OD vs. r_H…O correlation curves, respectively. The internal modes of the iodate ions of the title compounds are discussed with respect to their coupling with the librations of the hydrate H₂O molecules, the distortion of the IO₃^– ions, and the influence of the lattice potential.     

Reaktionen des [η2-{P–PtBu2}Pt(PPh3)2] und [η2-{P–PtBu2}Pt(dppe)] mit Metallcarbonylen. Bildung von [η2-{(CO)5M · PPtBu2}Pt(PPh3)2] (M = Cr,W) und [η2-{(CO)5Cr · PPtBu2}Pt(dppe)]

Coordination Chemistry of P-rich Phosphanes and Silylphosphanes. XVI [1] Reactions of [g²-{P–P^tBu₂}Pt(PPh₃)₂] and [g²-{P–P^tBu₂}Pt(dppe)] with Metal Carbonyls. Formation of [g²-{(CO)₅M · PP^tBu₂}Pt(PPh₃)₂] (M = Cr, W) and [g²-{(CO)₅Cr · PP^tBu₂}Pt(dppe)] [η²-{P–P^tBu₂}Pt(PPh₃)₂] 4 reacts with M(CO)₅ · THF (M = Cr, W) by adding the M(CO)₅ group to the phosphinophosphinidene ligand yielding [η²-{(CO)₅Cr · PP^tBu₂}Pt(PPh₃)₂] 1 , or [η²-{(CO)₅W · PP^tBu₂}Pt(PPh₃)₂] 2 , respectively. Similarly, [η²-{P–P^tBu₂}Pt(dppe)] 5 yields [η²-{(CO)₅Cr · PP^tBu₂}Pt(dppe)] 3 . Compounds 1 , 2 and 3 are characterized by their ¹H- and ³¹P-NMR spectra, for 2 and 3 also crystal structure determinations were performed. 2 crystallizes in the monoclinic space group P2₁/n (no. 14) with a = 1422.7(1) pm, b = 1509.3(1) pm, c = 2262.4(2) pm, β = 103.669(9)°. 3 crystallizes in the triclinic space group P1 (no. 2) with a = 1064.55(9) pm, b = 1149.9(1) pm, c = 1693.2(1) pm, α = 88.020(8)°, β = 72.524(7)°, γ = 85.850(8)°.     

Variable Bonding Modes of Pyrimidine‐2‐thione in PdII/PtII Complexes [M(η2‐N,S‐pymS)(η1‐S‐pymS)(PPh3)] and [M(η1‐S‐pymS)2(L‐L)] (L‐L = dppm,dppe)

Reactions of pyrimidine‐2‐thione (HpymS) with Pd^II/Pt^IV salts in the presence of triphenyl phosphine and bis(diphenylphosphino)alkanes, Ph₂P‐(CH₂)_m‐PPh₂ (m = 1, 2) have yielded two types of complexes, viz. a) [M(η²‐N, S‐ pymS)(η¹‐S‐ pymS)(PPh₃)] (M = Pd, 1 ; Pt, 2 ), and (b) [M(η¹‐S‐pymS)₂(L‐L)] {L‐L, M = dppm (m = 1) Pd, 3 ; Pt, 4 ; dppe (m = 2), Pd, 5 ; Pt, 6 }. Complexes have been characterized by elemental analysis (C, H, N), NMR spectroscopy (¹H, ¹³C, ³¹P), and single crystal X‐ray crystallography ( 1 , 2 , 4 , and 5 ). Complexes 1 and 2 have terminal η¹‐S and chelating η²‐N, S‐modes of pymS⁻, while other Pd/Pt complexes have only terminal η¹‐S modes. The solution state ³¹P NMR spectral data reveal dynamic equilibrium for the complexes 3 , 5 and 6 , whereas the complexes 1 , 2 and 4 are static in solution state.     

CaRhIn with TiNiSi Type Structure and CaTIn2 (T = Rh,Ir) with a New Filled Version of the Zintl Phase CaIn2

CaRhIn, CaRhIn₂, and CaIrIn₂ were synthesized by reacting the elements in glassy carbon crucibles under an argon atmosphere in a high‐frequency furnace. CaRhIn adopts the TiNiSi structure: Pnma, a = 730.0(4) pm, b = 433.1(2) pm, c = 828.8(4) pm, wR2 = 0.0707, 630 F² values, 20 variables. The CaRhIn structure consists of strongly puckered Rh₃In₃ hexagons with Rh–In distances ranging from 273 to 276 pm. Due to the strong puckering each rhodium atom has a distorted tetrahedral indium environment. The calcium atoms fill the channels within the three‐dimensional [RhIn] polyanion. CaRhIn₂ and CaIrIn₂ crystallize with a new structure type: Pnma, a = 1586.2(3) pm, b = 781.4(2) pm, c = 570.9(1) pm, wR2 = 0.0385, 1699 F² values, 44 variables for CaRhIn₂, and Pnma, a = 1588.7(3) pm, b = 780.8(1) pm, c = 574.0(1) pm, wR2 = 0.0475, 1661 F² values, 44 variables for CaIrIn₂. The structures of CaRhIn₂ and CaIrIn₂ can be described as an orthorhombically distorted rhodium respectively iridium filled CaIn₂. The motif of transition metal filling is similar to that found in MgCuAl₂ type compounds CaTIn₂ (T = Pd, Pt, Au) and SrTIn₂ (T = Rh, Pd, Ir, Pt), but constitute a different tiling. Semi‐empirical band structure calculations for CaRhIn and CaRhIn₂ reveal strong bonding In–In and Rh–In but weaker Ca–Rh and Ca–In interactions. Magnetic susceptibility and resistivity measurements of compact polycrystalline samples of CaRhIn₂ indicate weak Pauli paramagnetism and metallic conductivity with a room temperature value for the specific resistivity of 230 ± 50 μΩcm.     

Ein neuartiges Diorganylzinn(IV)-Komplexkation als Gastspezies in einer ionischen Harnstoff-Einschlußverbindung: Bildung und Struktur von [trans-Me2Sn{OC(NH2)2}4]2+ · 2 (MeSO2)2N7 · 6 (NH2)2CO

Polysulfonylamines. CVIII. A Novel Diorganyltin(IV) Complex Cation as Guest Species in an Ionic Urea Inclusion Compound: Formation and Structure of [ trans -Me₂Sn{OC(NH₂)₂}₄]²⁺ · 2 (MeSO₂)₂N⁷ · 6 (NH₂)₂CO The title compound (triclinic, space group P 1, Z = 1, X-ray analysis at –130 °C) was fortuitously obtained during an attempt to complex the known dimeric hydroxide [Me₂Sn(A)(μ-OH)]₂, where A⁷ = (MeSO₂)₂N⁷, with four equivalents of urea. The trans-octahedral and crystallographically centrosymmetric [Me₂Sn(urea)₄]²⁺ cation (Sn–O 221.6 and 223.7 pm, cis-angles in the range 90 ± 1.5°) is the first structurally authenticated [R₂Sn(L)₄]²⁺ complex featuring a urea-type ligand L. In the crystal, these cations are sandwiched between and hydrogen-bonded to puckered layers corresponding to the [011] family of planes. Each layer is constructed from rows of A⁷ anions, which extend parallel to the x axis and are alternatingly cross-linked by a planar zig-zag tape of urea molecules or by a pair of inversion-related urea zig-zag tapes displaying a non-planar roof profile. The structure contains 23 crystallographically independent hydrogen bonds N–H…O/N, comprising two intracationic N–H…O bonds, two and four N–H…O bonds leading to the two respective types of urea tapes, eight N–H…O bonds and one N–H…N⁷ bond connecting the urea tapes to the electronegative atoms of the anions, and six N–H…O interactions between the ligands of the complex guest cation and C=O or S=O acceptors within the layers of the host lattice. The anion A⁷ accepts a total of twelve H bonds and adopts a previously unreported conformation.     

Vierkernige Clusterkomplexe vom Typ [MM′(AuPR3)2(μ‐H)(μ‐PCy2)(μ4‐PCy)(CO)6] (M,M′ = Mn,Re; R = Ph,Cy, Et): Synthese,Struktur und Topomerisierung

Tetranuclear Cluster Complexes of the Type [MM′(AuR₃)₂(μ‐H)(μ‐PCy₂)(μ₄‐PCy)(CO)₆] (M,M′ = Mn, Re; R = Ph, Cy, Et): Synthesis, Structure, and Topomerisation The dirhenium complex [Re₂(μ‐H)(μ‐PCy₂)(CO)₇(ax‐H₂PCy)] ( 1 ) reacts at room temperature in thf solution with each two equivalents of the base DBU and of ClAuPR₃ (R = Ph, Cy, Et) in a photochemical reaction process to afford the tetranuclear clusters [Re₂(AuPR₃)₂(μ‐H)(μ‐PCy₂)(μ₄‐PCy)(CO)₆] (R = Ph ( 2 ), Cy ( 3 ), Et ( 4 )) in yields of 35–48%. The homologue [Mn₂(μ‐H)(μ‐PCy₂)(CO)₇(ax‐H₂PCy)] ( 5 ) leads under the same reaction conditions to the corresponding products [Mn₂(AuPR₃)₂(μ‐H)(μ‐PCy₂)(μ₄‐PCy)(CO)₆] (R = Ph ( 6 ), Et ( 8 )). Also [MnRe(μ‐H)(μ‐PCy₂)(CO)₇(ax/eq‐H₂PCy)] ( 9 ) reacts under formation of [MnRe(AuPR₃)₂(μ‐H)(μ‐PCy₂)(μ₄‐PCy)(CO)₆] (R = Ph ( 10 ), Et ( 11 )). All new cluster complexes were identified by means of ¹H‐NMR, ³¹P‐NMR and ν(CO)‐IR spectroscopic measurements. 2 , 4 and 10 have also been characterized by single crystal X‐ray structure analyses with crystal parameters: 2 triclinic, space group P 1, a = 12.256(4) Å, b = 12.326(4) Å, c = 24.200(6) Å, α = 83.77(2)°, β = 78.43(2)°, γ = 68.76(2)°, Z = 2; 4 monoclinic, space group C2/c, a = 12.851(3) Å, b = 18.369(3) Å, c = 40.966(8) Å, β = 94.22(1)°, Z = 8; 10 triclinic, space group P 1, a = 12.083(1) Å, b = 12.185(2) Å, c = 24.017(6) Å, α = 83.49(29)°, β = 78.54(2)°, γ = 69.15(2)°, Z = 2. The trapezoid arrangement of the metal atoms in 2 and 4 show in the solid structure trans‐positioned an open and a closed Re…Au edge. In solution these edges are equivalent and, on the ³¹P NMR time scale, represent two fluxional Re–Au bonds in the course of a topomerization process. Corresponding dynamic properties were observed for the dimanganese compounds 6 and 8 but not for the related MnRe clusters 10 and 11 . 2 and 4 are the first examples of cluster compounds with a permanent Re–Au bond valence isomerization.