Umsetzung von C(NMe2)4 mit Ni(CO)4 – Synthesen und Strukturen von [C(NMe2)3][(CO)3NiC(O)NMe2], [C(NMe2)3]2[Ni5(CO)12] und [C(NMe2)3]3[Ni6(CO)12][O2CNMe2]

Reaction of C(NMe₂)₄ with Ni(CO)₄ – Syntheses and Structures of [C(NMe₂)₃][(CO)₃NiC(O)NMe₂], [C(NMe₂)₃]₂[Ni₅(CO)₁₂], and [C(NMe₂)₃]₃[Ni₆(CO)₁₂][O₂CNMe₂] The reaction of C(NMe₂)₄ with Ni(CO)₄ in THF produces the carbamoyl complex [C(NMe₂)₃][(CO)₃NiC(O)NMe₂] ( 1 ); side products are the purple cluster compound [C(NMe₂)₃]₂[Ni₅(CO)₁₂] · THF ( 2 · THF) and the red cocristallization product [C(NMe₂)₃]₃[Ni₆(CO)₁₂][O₂CNMe₂] ( 3 ). All compounds were studied by X‐ray diffraction analyses. The cations of 3 are all disordered but not those of 1 and 2 . The unit cell of 1 contains two crystallographically independent anions (I and II) which differ in the dihedral angle between the plane of the carbamoyl ligand and the plane defined by the atoms C_Carbamoyl–Ni–CO amounting 0° in the anion I and 18° in the anion II.     

Synthesis, Electrochemistry and Crystal Structure of the [Ni36Pt4(CO)45]6− and [Ni37Pt4(CO)46]6− Hexaanions

The [Ni₃₆Pt₄(CO)₄₅]^6- and [Ni₃₇Pt₄(CO)₄₆]^6- clusters have been obtained in mixture upon reaction in acetonitrile of [Ni₆(CO)₁₂]^2- salts with K₂PtCl₄ in a 2.5:1 molar ratio. The two hexaanions were indistinguishable by spectroscopic techniques. Crystallization of their trimethylbenzylammonium salts led to crystals of composition 0.5[NMe₃CH₂Ph]₆[Ni₃₆Pt₄(CO)₄₅]-0.5[NMe₃CH₂Ph]₆[Ni₃₇Pt₄(CO)₄₆]·C₃H₈O, hexagonal,space group P6₃ (No. 173), a=17.853(9), c=27.127(13) Å, Z=2; final R=0.057. The metal core of the [Ni₃₆Pt₄(CO)₄₅]^6- anion consists of a Pt₄ tetrahedron fully encapsulated in a shell of 36 Ni atoms belonging to a very distorted and incomplete ₅ tetrahedron. The [Ni₃₇Pt₄(CO)₄₆]^6- hexaanion derives from the former by capping the unique triangular face of the metal polyhedron with an additional Ni(CO) fragment. The [Ni₃₆Pt₄(CO)₄₅]^6--[Ni₃₇Pt₄(CO)₄₆]^6- mixture is rapidly degraded to the known [Ni₉Pt₃(CO)₂₁]^4- cluster by exposure to carbon monoxide. Its reaction with protic acids initially affords the corresponding [H_6-nNi₃₆Pt₄(CO)₄₅]^n--[H_6-nNi₃₇Pt₄(CO)₄₆]^n- (n=5, 4) derivatives, and eventually leads to rearrangement to the known [H_6-n Ni₃₈Pt₆(CO)₄₈]^n- species. Both [Ni₃₆Pt₄(CO)₄₅]^6--[Ni₃₇Pt₄(CO)₄₆]^6- and [HNi₃₆Pt₄(CO)₄₅]^5--[HNi₃₇Pt₄(CO)₄₆]^5- mixtures have been chemically and electrochemically reduced to their corresponding [Ni₃₆Pt₄(CO)₄₅]^n--[Ni₃₇Pt₄(CO)₄₆]^n- (n=7–9) and [HNi₃₆Pt₄(CO)₄₅]^n--[HNi₃₇Pt₄(CO)₄₆]^n- (n=6–8) mixtures.     

Capping [H<Subscript>8−n</Subscript>Ni<Subscript>42</Subscript>C<Subscript>8</Subscript>(CO)<Subscript>44</Subscript>]<Superscript>n−</Superscript> (n = 6, 7, 8) Octa-carbide Carbonyl Nanoclusters with [Ni(CO)] and [CuCl] Fragments

The reactions of [Ni₁₆(C₂)₂(CO)₂₃]^4? and [Ni₃₈C₆(CO)₄₂]^6? with CuCl afforded mixtures of the previously reported [HNi₄₂C₈(CO)₄₄(CuCl)]^7? bimetallic octa-carbide cluster and the new [HNi₄₃C₈(CO)₄₅]^7? and [HNi₄₄C₈(CO)₄₆]^7? homo-metallic octa-carbides. The three species have very similar properties resulting always in co-crystals such as [NMe₄]₇[HNi_42+2xC₈(CO)_44+2x(CuCl)_1?x]·6.5MeCN (x = 0.14) (86% [HNi₄₂C₈(CO)₄₄(CuCl)]^7?, 14%[HNi₄₃C₈(CO)₄₅]^7?/[HNi₄₄C₈(CO)₄₆]^7?) and [NMe₄]₇[HNi_42+2xC₈(CO)_44+2x(CuCl)_1?x]·5.5MeCN (x = 0.30) (70% [HNi₄₂C₈(CO)₄₄(CuCl)]^7?, 30% [HNi₄₃C₈(CO)₄₅]^7?/[HNi₄₄C₈(CO)₄₆]^7?). The new homo-metallic octa-carbides can be obtained free from the Ni–Cu octa-carbido cluster by reacting [Ni₁₀(C₂)(CO)₁₆]^2? in thf with a stoichiometric amount of CuCl, and crystals of [NMe₄]₆[H₂Ni_43+xC₈(CO)_45+x]·6MeCN (x = 0.72), which contain [H₂Ni₄₄C₈(CO)₄₆]^6? (72%) and [H₂Ni₄₃C₈(CO)₄₅]^6? (28%), have been obtained. Despite the different charges and compositions, these anions display almost identical structures, which are also closely related to those previously reported for the bimetallic Ni–Cd octa-carbido clusters [Ni_42+xC₈(CO)_44+x(CdCl)]^7? and [HNi_42+xC₈(CO)_44+x(CdBr)]^6?. Indeed, all these clusters are based on the same Ni₄₂C₈ cage decorated by miscellaneous [CdX]⁺ (X = Cl, Br), [CuCl] and [Ni(CO)] fragments.     

Formation of Unusual Complexes from the Reaction of [C(NMe2)3][(CO)4Fe{C(O)NMe2}] with InMe3; Crystal Structures of [C(NMe2)3]3[Fe2(CO)6(μ‐CO){μ‐InFe(CO)4(μ‐O2CNMe2)InFe(CO)4}] and [C(NMe2)3]2[{(CO)4Fe}2In(O2CNMe2)]·THF

The carbamoyl complex [C(NMe₂)₃][(CO)₄Fe{C(O)NMe₂}] ( 1 ) reacts with InMe₃ under loss of the methyl groups to produce a variety of compounds from which only the anionic cluster complexes [C(NMe₂)₃]₃[Fe₂(CO)₆(μ‐CO){μ‐InFe(CO)₄(μ‐O₂CNMe₂)InFe(CO)₄}] ([C N ₃]₃[ 2 ]) and [C(NMe₂)₃]₂[{(CO)₄Fe}₂In(O₂CNMe₂)]·THF ([C N ₃]₂[ 3 ]·THF) could be crystallized and characterized by X‐ray analyses. The anion [ 2 ]^3? has a Fe₂(CO)₉‐like structure and both anions contain the carbaminato ligand either in a bridging or in a chelating function.     

Structural investigations of alumino-metalloaminocarbene complexes

[Al(NMe₂)₃]₂ combines with Fe(CO)₅ and Mn₂(CO)₁₀ forming bimetallic compounds Fe₂(CO)₈[C(NMe₂)OAl(NMe₂)₂]₂ and Mn₂(CO)₉[C(NMe₂)OAl₂-(NMe₂)₅]. X-ray diffraction analyses reveal the formation of aluminometallocarbene compounds with central connectivities, MC[NMe₂)][OAl(NMe₂)(μ-NMe₂)₂].     

Neue Phosphor-verbrückte Übergangsmetallcarbonyl-Komplexe Die Kristallstrukturen von [Re2(CO)7(PtBu)3], [Co4(CO)10(PtBu)2], [Ir4(CO)6(PtBu)6] und [Ni4(CO)10(PiPr)6]

New Phosphorus-bridged Transition Metal Carbonyl Complexes. The Crystal Structures of [Re₂(CO)₇(P^tBu)₃], [Co₄(CO)₁₀(P^tBu)₂], [Ir₄(CO)₆(P^tBu)₆], and [Ni₄(CO)₁₀(PⁱPr)₆], (P^tBu)₃ reacts with [Mn₂(CO)₁₀], [Re₂(CO)₁₀], [Co₂(CO)₈] and [Ir₄(CO)₁₂] to form the multinuclear complexes [M₂(CO)₇(P^tBu)₃] (M = Re ( 1 ), Mn ( 5 )), [Co₄(CO)₁₀(P^tBu)₂] ( 2 ) and [Ir₄(CO)₆(P^tBu)₆] ( 3 ). The reaction of (PⁱPr)₃ with [Ni(CO)₄] leads to the tetranuclear cluster [Ni₄(CO)₁₀(PⁱPr)₆] ( 4 ). The complex structures were obtained by X-ray single crystal structure analysis: ( 1 : space group P1 (Nr. 2), Z = 2, a = 917.8(3) pm, b = 926.4(3) pm, c = 1 705.6(7) pm, α = 79.75(3)°, β = 85.21(3)°, γ = 66.33(2)°; 2 : space group C2/c (Nr. 15), Z = 4, a = 1 347.7(6) pm, b = 1 032.0(3) pm, c = 1 935.6(8) pm, β = 105.67(2)°; 3 : space group P1 (Nr. 2), Z = 4, a = 1 096.7(4)pm, b = 1 889.8(10)pm, c = 2 485.1(12) pm, α = 75.79(3)°, β = 84.29(3)°, γ = 74.96(3)°; 4 : space group P2₁/c (Nr. 14), Z = 4, a = 2 002.8(5) pm, b = 1 137.2(8) pm, c = 1 872.5(5) pm, β = 95.52(2)°).     

New Ni–Pt Carbonyl Clusters with a Tetrahedron of Platinum Atoms Encapsulated in an Incomplete Tetrahedron of Nickel Atoms: [Ni36Pt4(CO)45]6− and [Ni37Pt4(CO)46]6−

A fully encapsulated Pt ₄ tetrahedron in an incomplete tetrahedron of 36 nickel atoms is present in [Ni₃₆Pt₄(CO)₄₅]⁶⁻ ( 1 ; see picture for the metal framework), which is obtained as an inseparable mixture with [Ni₃₇Pt₄(CO)₄₆]⁶⁻ ( 2 ) by reaction of [Ni₆(CO)₁₂]²⁻ with K₂[PtCl₄]. The trimethylbenzylammonium salts of 1 and 2 cocrystallize in a 1:1 ratio. The additional Ni atom of 2 caps the truncated vertex of 1 .     

Surface-Mediated Organometallic Synthesis: High-Yield Syntheses of [Ir4(CO)12], [Ir6(CO)15]2−, and [Ir8(CO)22]2− by Controlled Reduction of Silica-Supported IrCl3 or [Ir(cyclooctene)2(μ-Cl)]2 in the Presence of Na2CO3 or K2CO3

The controlled reductive carbonylation under 1 atm. of CO of [Ir(cyclooctene)₂(μ-Cl)]₂, supported on a silica surface added with an alkali carbonate such as Na₂CO₃ or K₂CO₃, can be directed toward the formation of [Ir₄(CO)₁₂], K₂[Ir₆(CO)₁₅] or K₂[Ir₈(CO)₂₂] by controlling (i) the nature and amount of alkali carbonate, (ii) the amount of surface water, and (iii) the temperature. [Ir₄(CO)₁₂] can also be prepared by direct controlled reductive carbonylation of IrCl₃ supported on silica in the presence of well controlled amounts of Na₂CO₃. These efficient silica-mediated syntheses are comparable to conventional synthetic methods carried out in solution or on the MgO surface. Like in strongly basic solution or on the MgO surface, the initially formed [Ir₄(CO)₁₂], the first step of nucleation which does not require a strong basicity of the silica surface, gives in a second time sequentially [Ir₈(CO)₂₂]^2? and [Ir₆(CO)₁₅]^2? according to reaction conditions and basicity of the silica surface.     

Structural Studies on some Iodoantimonate and Iodobismuthate Anions

The reaction between BiI₃ and two equivalents of dmpu (dmpu = N,N′-dimethylpropylene urea) in thf (tetrahydrofuran) or toluene affords dark red crystals of the complex [Bi(dmpu)₆][Bi₃I₁₂] which was characterised by X-ray crystallography and consists of octahedral [Bi(dmpu)₆]³⁺ cations and [Bi₃I₁₂]^3? anions both with 3 symmetry. An analogous reaction between SbI₃ and dmpu afforded orange crystals of what is probably a hydrolysis product, [C₅NH₆]₂[H(dmpu)₂][Sb₂I₉], which was also characterised by X-ray crystallography and contains a face-shared bioctahedral [Sb₂I₉]^3? anion with two pyridinium cations and a hydrogen bonded [H(dmpu)₂]⁺ cation. [CH₂?C(C₆H₄-4-NO₂)CH₂NMe₃]I and one equivalent of SbI₃ afforded the orange crystalline complex [CH₂?C(C₆H₄-4-NO₂)CH₂NMe₃]₃[Sb₂I₉] an X-ray crystallographic study of which revealed a face-shared bioctahedral [Sb₂I₉]^3? anion similar to that present in [C₅NH₆]₂[H(dmpu)₂][Sb₂I₉]. Four equivalents of BiI₃ and [CH₂?C(C₆H₄-4-NO₂)CH₂NMe₃]I afforded the complex [CH₂?C(C₆H₄-4-NO₂)CH₂NMe₃]₃[Bi₃I₁₂], the [Bi₃I₁₂]^3? anion being essentially identical to that encountered in [Bi(dmpu)₆][Bi₃I₁₂]. [CH₃(CH₂)₂COS(CH₂)₂NMe₃]I and four equivalents of SbI₃ yielded orange crystals of the complex [CH₃(CH₂)₂COS(CH₂)₂NMe₃]₄[Sb₈I₂₈] which was also characterised by X-ray crystallography and shown to contain a new structural type of [E₈X₂₈]^4? anion (E = As, Sb, Bi; X = halide).     

New Bimetallic Ni–Rh Carbonyl Clusters: Synthesis and X-ray Structure of the [Ni7Rh3(CO)18]3?, [Ni3Rh3(CO)13]3? and [NiRh8(CO)19]2? Cluster Anions

The reaction of the [Ni₆(CO)₁₂]²⁻ dianion with [Rh(COD)Cl]₂ (COD = cyclooctadiene) in acetone affords a mixture of bimetallic Ni–Rh clusters, mainly consisting of the new [Ni₇Rh₃(CO)₁₈]³⁻ and [Ni₈Rh(CO)₁₈]³⁻ trianions. A study of the reactivity of [Ni₇Rh₃(CO)₁₈]³⁻ led to isolation of the new [Ni₃Rh₃(CO)₁₃]³⁻ and [NiRh₈(CO)₁₉]²⁻ anions. All these new bimetallic Ni–Rh carbonyl clusters have been isolated in the solid state as tetrasubstituted ammonium salts and have been characterised by elemental analysis, X-ray diffraction studies, ESI-MS and electrochemistry. The unit cell of the [NEt₄]₃[Ni₇Rh₃(CO)₁₈] salt contains two orientationally-disordered ν₂-tetrahedral [Ni₇Rh₃(CO)₁₈]³⁻ trianions with occupancy factors of 0.75 and 0.25. Besides, their inner Ni₃Rh₃ octahedral moieties show two cis sites purely occupied by Rh atoms, two trans sites purely occupied by Ni atoms and the remaining two cis sites are disordered Ni and Rh sites with respective occupancy fraction of 0.5. At difference from the parent [Ni₇Rh₃(CO)₁₈]³⁻, the octahedral [Ni₃Rh₃(CO)₁₃]³⁻ displays an ordered distribution of Ni and Rh atoms in two staggered triangles. The [NiRh₈(CO)₁₉]²⁻ dianion adopts an isomeric metal frame with respect to that of the [PtRh₈(CO)₁₉]²⁻ congener. As a fallout of this work, new high-yield synthesis of the known [Ni₆Rh₃(CO)₁₇]³⁻ and [Ni₆Rh₅(CO)₂₁]³⁻, as well as other currently-investigated bimetallic Ni–Rh clusters have been obtained.     

Synthese und Struktur der Phosphor-verbrückten Übergangsmetallkomplexe [Fe2(CO)6(PR)6] (R = tBu,iPr), [Fe2(CO)4(PiPr)6], [Fe2(CO)3Cl2(PtBu)5], [Co4(CO)10(PiPr)3], [Ni5(CO)10(PiPr)6] und [Ir4(C8H12)4Cl2(PPh)4]

Synthesis and Structure of the Phosphorus-bridged Transition Metal Complexes [Fe₂(CO)₆(PR)₆] (R = ^tBu, ⁱPr), [Fe₂(CO)₄(PⁱPr)₆], [Fe₂(CO)₃Cl₂(P^tBu)₅], [Co₄(CO)₁₀(PⁱPr)₃], [Ni₅(CO)₁₀(PⁱPr)₆], and [Ir₄(C₈H₁₂)₄Cl₂(PPh)₄] (P^tBu)₃ and (PⁱPr)₃ react with [Fe₂(CO)₉] to form the dinuclear complexes [Fe₂(CO)₆(PR)₆] (R = ^tBu: 1 ; ⁱPr: 2 ). 2 is also formed besides [Fe₂(CO)₄(PⁱPr)₆] ( 3 ) in the reaction of [Fe(CO)₅] with (PⁱPr)₃. When PⁱPr(P^tBu)₂ and PⁱPrCl₂ are allowed to react with [Fe₂(CO)₉] it is possible to isolate [Fe₂(CO)₃Cl₂(P^tBu)₅] ( 4 ). The reactions of (PⁱPr)₃ with [Co₂(CO)₈] and [Ni(CO)₄] lead to the tetra- and pentanuclear clusters [Co₄(CO)₁₀(PⁱPr)₃] ( 5 ), [Ni₄(CO)₁₀(PⁱPr)₆] [2] and [Ni₅(CO)₁₀(PⁱPr)₆] ( 6 ). Finally the reaction of [Ir(C₈H₁₂)Cl]₂ with K₂(PPh)₄ leads to the complex [Ir₄(C₈H₁₂)₄Cl₂(PPh)₄] ( 7 ). The structures of 1–7 were obtained by X-ray single crystal structure analysis (1: space group P2₁/c (Nr. 14), Z = 8, a = 1 758.8(16) pm, b = 3 625.6(18) pm, c = 1 202.7(7) pm, β = 90.07(3)°; 2 : space group P1 (Nr. 2), Z = 1, a = 880.0(2) pm, b = 932.3(3) pm, c = 1 073.7(2) pm, α = 79.07(2)°, β = 86.93(2)°, γ = 72.23(2)°; 3 : space group Pbca (Nr. 61), Z = 8, a = 952.6(8) pm, b = 1 787.6(12) pm, c = 3 697.2(30) pm; 4 : space group P2₁/n (Nr. 14), Z = 4, a = 968.0(4) pm, b = 3 362.5(15) pm, c = 1 051.6(3) pm, β = 109.71(2)°; 5 : space group P2₁/n (Nr. 14), Z = 4, a = 1 040.7(5) pm, b = 1 686.0(5) pm, c = 1 567.7(9) pm, β = 93.88(4)°; 6 : space group Pbca (Nr. 61), Z = 8, a = 1 904.1(8) pm, b = 1 959.9(8) pm, c = 2 309.7(9) pm. 7 : space group P1 (Nr. 2), Z = 2, a = 1 374.4(7) pm, b = 1 476.0(8) pm, c = 1 653.2(9) pm, α = 83.87(4)°, β = 88.76(4)°, γ = 88.28(4)°).     

Contribution to Halo‐Chalcogenates Chemistry

Abstract. By direct reactions of selenium with halogen and trimethylphenylammonium halogenide and tetraphenylphosphonium, ethyltriphenylphosphonium, and methyltriphenylphosphonium bromides, the tetrahalogenidoselenates(II) – bis(trimethylphenylammonium)tetrabromidoselenate(II) bromide, [NPhMe₃]₂[SeBr₄] · [NPhMe₃]Br, a mixed bis(trimethylphenylammonium) tetra(bromido/chlorido)selenate(II), [NPhMe₃]₂[SeBr_4–xCl_x] · [NPhMe₃]₂SeBr_1–yCl_y], [NPhMe₃]₂[SeBr_4–xCl_x],the haxahalogenidodiselenates(II) – bis(trimethylphenylammonium) hexabromidodiselenate(II), [NPhMe₃]₂[Se₂Br₆], bis(trimethylphenylammonium) hexachloridodiselenate(II), [NPhMe₃]₂[Se₂Cl₆], a mixed bis(trimethylphenylammonium) bromido/chlorido‐diselenate(II), [NPhMe₃]₂[Se₂Br₅Cl], bis(tetraphenylphosphonium) hexabromidodiselenate(II), [PPh₄]₂[Se₂Br₆], bis(ethyltriphenylphosphonium) hexabromidodiselenate(II), [PEtPh₃]₂[Se₂Br₆], and bis(methyltriphenylphosphonium) hexabromidodiselenate(II), [PMePh₃]₂[Se₂Br₆], were prepared. By the reaction of selenium with bromine in acetonitrile in the presence of trimethylphenylammonium, benzyltrimethylammonium, and tetramethylammonium bromides, the salts of the unique bromidoselenate(I) anions – bis(trimethylphenylammonium) hexabromidotetraselenate(I), [NPhMe₃]₂[Se₄Br₆], bis(benzyltrimethylammonium) hexabromidotetraselenate(I), [NBzMe₃]₂[Se₄Br₆], and bis(tetramethylammonium) octadecabromidohexadecaselenate(I), [NMe₄]₂[Se₁₆Br₁₈], were isolated. First mixed‐valence bromidoselenates(II/I) – bis(tetraethylammonium) octabromidotriselenate(II){dibromidodiselenate(I)}, [NEt₄]₂[Se₃Br₈(Se₂Br₂)], bis(tetraphenylphosphonium) hexabromidodiselenate(II)‐bis{dibromidodiselenate(I)}, [PPh₄]₂[Se₂Br₆(Se₂Br₂)₂], and tetrakis(tetramethylammonium) bis{decabromidotetraselenate(II)}‐bis{dibromidodiselenate(I)}, [(CH₃)₄N]₄[(Se₄Br₁₀)₂(Se₂Br₂)₂] – were synthesized. Mixed bis(trimethylphenylammonium) hexabromidoselenate/tellurate(IV), [NPhMe₃]₂[Se_0.75Te_0.25Br₆], catena‐poly[(di‐μ‐bromidobis‐{tetrabromidoselenate/tellurate(IV)})‐ μ‐bromine], [NPhMe₃]_2n[Se_1.5Te_0.5Br₁₀ · Br₂]_n were isolated. First mixed‐valence bromidoselenate(IV/I)‐bis(trimethylphenylammonium) hexabromidoselenate(IV)‐bis{dibromidodiselenate(I)}, [NPhMe₃]₂[SeBr₆(Se₂Br₂)₂], a number of mixed bromidochalcogenates(IV/I) – bis(trimethylphenylammonium), bis(tetraethylphosphonium), bis(ethyltriphenylphosphonium) hexabromidotellurates(IV)‐bis{dibromidodiselenates(I)}, [NPhMe₃]₂[TeBr₆(Se₂Br₂)₂], [PEt₄]₂[TeBr₆(Se₂Br₂)₂], [PEtPh₃]₂[TeBr₆(Se₂Br₂)₂], bis(triethylmethylammonium) hexabromidotellurate(IV)‐tris{dibromidodiselenate(I)}, [NMeEt₃]_2n[TeBr₆(Se₂Br₂)₃]_n, were synthesized. Mixed‐valence bromidoselenate(IV/II) – bis(methyltriphenylphosphonium) hexabromidoselenate(IV)‐bis{dibromidoselenate(II)},[PMePh₃]₂[SeBr₆(SeBr₂)₂], received by direct synthesis and two mixed‐valence bromidochalcogenates(IV/II) – bis(methyltriphenylphosphonium) and bis(tetrapropylammonium) hexabromidotellurates(IV)‐selenates(II), [PMePh₃]₂[TeBr₆(SeBr₂)₂] and [NⁿPr₄]₂[TeBr₆(SeBr₂)₂], were synthesized from elemental selenium, tellurium dioxide, and corresponding onium bromide. The structures of all compounds were determined by X‐ray diffraction.     

Iron(0), rhodium(I) and palladium(II) complexes with p‐(N,N‐dimethylaminophenyl) diphenylphosphine and the application of the palladium complex as a catalyst for the Suzuki–Miyaura cross‐coupling reaction

The reaction of p‐(N,N‐dimethylaminophenyl)diphenylphosphine [PPh₂(p‐C₆H₄NMe₂)] with [Fe₃(CO)₁₂], [Rh(CO)₂Cl]₂ and PdCl₂ resulted in three new mononuclear complexes, {Fe(CO)₄[η¹‐(P)‐PPh₂(p‐C₆H₄NMe₂)]} ( 1a ), trans‐{Rh(CO)Cl[η¹‐(P)‐PPh₂(p‐C₆H₄NMe₂)]₂} ( 2 ) and trans‐{PdCl₂[η¹‐(P)‐PPh₂(p‐C₆H₄NMe₂)]₂} ( 3 ), respectively. A small amount of dinuclear nonmetal‐metal bonded complex, {Fe₂(CO)₈[µ‐(P,N)‐PPh₂(p‐C₆H₄NMe₂)]} ( 1b ), was also isolated as a side product in the reaction of [Fe₃(CO)₁₂]. The complexes were characterized by elemental analyses, mass, IR, UV–vis, ¹H, ¹³C (except 1b) and ³¹P{¹H} NMR spectroscopy. The Pd complex 3 effectively catalyzes the Suzuki–Miyaura cross‐coupling reactions of aryl halides with arylboronic acids in water–isopropanol (1:1) at room temperature. Excellent yields (up to 99% isolated yield) were achieved. The effects of different solvents, bases, catalyst quantities were also evaluated. Copyright © 2011 John Wiley & Sons, Ltd.     

Über die Reaktionen von CH2=P(NMe2)3 mit Fe(CO)5, Cr(CO)6 und CS2; Molekülstrukturen von [MeP(NMe2)3][(CO)5CrC(O)CH=P(NMe2)3] und (CO)4Fe=C(OMe)CH=P(NMe2)3

The Reactions of CH₂=P(NMe₂)₃ with Fe(CO)₅, Cr(CO)₆, and CS₂; Molecular Structures of [MeP(NMe₂)₃][(CO)₅CrC(O)CH=P(NMe₂)₃], and (CO)₄Fe=C(OMe)CH=P(NMe₂)₃ The ylide CH₂=P(NMe₂)₃ ( 1 ) reacts with several binary transition metal carbonyls M(CO)_x to produce the corresponding salt like compounds [MeP(NMe₂)₃][(CO)_x–1MC(O)CH=P(NMe₂)₃] (M = Fe ( 3 ), Cr ( 4 )). The related reaction with CS₂ leads to the salt [MeP(NMe₂)₃][SC(S)CH=P(NMe₂)₃] ( 2 ). While 4 is thermally stable, 3 rapidly decomposes at room temperature with formation of [MeP(NMe₂)₃]₂[Fe₂(CO)₈] ( 8 ). Alkylation of 3 (at –50 °C) and 4 with MeSO₃CF₃ produces the related carbene complexes (CO)_x–1M=C(OMe)CH=P(NMe₂)₃ ( 5 ) and ( 6 ); the reaction of 3 with Me₃SiCl results in the formation of the carbene complex (CO)₄Fe=C(OSiMe₃)CH=P(NMe₂)₃ ( 7 ). 4 crystallizes in the space group P2₁2₁2₁ (No. 19) with a = 1111.1(2), b = 1476.1(3), c = 1823.1(4) pm and Z = 4. 5 crystallizes in the space group P2₁/n (No. 14) with a = 1303.6(3), b = 910.5(4), c = 1627.0(4) pm, β = 96.06(2)° and Z = 4. The compounds have been characterized by elemental analyses, NMR (¹H, ¹³C, ³¹P) and IR spectroscopy.     

Pyrolyses of the anion dihydridotetracarbonylrhenate. Crystal and molecular structure of bis(tetraethylammonium) μ-hydrido-dodecacarbonyl-triangulo-trirhenate(2—)

The pyrolyses of [NEt₄][H₂Re(CO)₄] in boiling n-heptane, n-octane and n-nonane are described. Mixtures of polynuclear carbonyl- and hydridocarbonylrhenium species are obtained, the principal products being [Re₄(CO)₁₆]^2?, [H₂Re₃(CO)₁₂], [H₃Re₃(CO)₁₀]^2?, [H₃Re₃O(CO)₉]^2? and [H₆Re₄(CO)₁₂]^2?. A red-orange crystalline species was isolated from the reaction in n-heptane and shown by X-ray diffraction to be [Net₄]₂[HRe₃(CO)₁₂]. It gives orthorhombic crystals, space group Pbca, with cell constants a 16.07(1), b 23.39(2), c 19.49(1) Å. The structure was solved by Patterson and Fourier methods and refined by least-squares up to a final R value of 0.061, for 1303 independent counter data. The anion [HRe₃(CO)₁₂]^2? contains an isosceles metal atom triangle, with two short edges of 3.014(3) and 3.018(3) Å and a long hydrogen-bridged edge of 3.125(3) Å.     

Substituted derivatives of [Fe2(CO)9] and [Ru2(CO)9] and their susceptibility to electrophilic attack: X-ray crystal structure of [Fe2(μ-Br)(CO)4{μ-(C6H5O)2PN(C2H5)P(OC6H5)2}2]PF6

Bis- and, in particular, tetra-substituted ditertiary phosphine and diphosphazane derivatives of [Fe₂(CO)₉] and [Ru₂(CO)₉], readily synthesised by reaction of the appropriate bidentate ligand with [Fe₂(CO)₉] and [Ru₃(CO)₁₂], respectively, are very susceptible to electrophilic attack by reagents such as halogens and protons; the solid state structure of one of the products [Fe₂(μ-Br)(CO)₄ {μ-(PhO)₂PN(Et)P(OPh)₂}₂]PF₆ has been determined by X-ray crystallography.     

The Representation of Electrical Conductances for Polyvalent Electrolytes by the Quint-Viallard Conductivity Equation. Part 3. Unsymmetrical 3:1, 1:3, 3:2, 4:1, 1:4, 4:2, 2:4, 1:5 1:6 and 6:1 Type Electrolytes. Dilute Aqueous Solutions of Rare Earth Salts, Various Cyanides and other Salts

Electrical conductivities of dilute aqueous solutions for unsymmetrical electrolytes of the type 3:1, 1:3, 3:2, 4:1, 1:4, 4:2, 2:4, 1:5 1:6 and 6:1 are reexamined in the framework of the Quint-Viallard conductivity equations, in order to obtain a uniform representation of their conductivities. The molar and equivalent limiting conductances were evaluated with ion association constants, which were treated as adjustable parameters. The derived values were compared with corresponding results from the literature. The following electrolytes are considered: rare earth (La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er) halides, perchlorides, nitrates and sulfates; hexamminecobalt and tris-ethylenediaminecobalt halides, perchlorides, nitrates and sulfates; [Ni₂(trien)₃]Cl₄, [Pt(pn)₃]Cl₄, [Co₂(trien)₃]Cl₆; cyanides K₃[Fe(CN)₆], K₃[Co(CN)₆], M₃[W(CN)₈] with M=Na, K, Rb, Cs; Ca₂[Fe(CN)₆], K₄[Fe(CN)₆], K₄[Mo(CN)₈], K₄[W(CN)₈], K₄[Ru(CN)₈], (Me₄N)₄[Fe(CN)₆], (Pr₄N)₄[Fe(CN)₆], K₄[Mo(CN)₈], (Me₄N)₄[Mo(CN)₈], (Et₄N)₄[Mo(CN)₈] and (Pr₄N)₄[Mo(CN)₈]; phosphates Na₄P₂O₇, Na₄P₄O₁₂, Na₅P₃O₁₀, Na₆P₆O₁₈ and (Me₄N)₄P₄O₁₂.     

Crystal structure of polynuclear pivalate Ni(II) complexes with butanediol

Using single crystal X-ray diffraction the structure of polynuclear [Ni₆(OH)₄(Piv)₇(HOC₄H₈O)(HPiv)₄], {K₄[Ni₁₂(CO₃)₂(Piv)₁₆(OH)₈(HOC₄H₈OH)₂]}HPiv, {[Ni₆(OH)₄(Piv)₆(HOC₄H₈O)(Me₂CO)(HOC₄H₈OH)₂]₄×(Piv)₄}, and {K[Ni₂L₂(Piv)₃]}_∞ complexes, where HOC₄H₈OH is 1,4-butanediol, HPiv is pivalic acid, and L is the anion of nitroxyl radical 2,2,5,5-tetramethyl-4-(3′,3′,3′-trifluoro-2′-oxy-1′-propenyl)-3-imidazolin-1-oxyl is determined.     

Re4(CO)12[μ3-InRe(CO)5]4 und Re2(CO)8[μ-InRe(CO)5]2-cluster aus dem reaktionssystem In/Re2(CO)10 in xylol

The thermally stable solids Re₂(CO)₈[μ-InRe(CO)₅]₂ and Re₄(CO)₁₂[μ₃-InRe(CO)₅]₄ could be obtained by treatment of In with Re₂(CO)₁₀ in a bomb tube. A mechanism of the formation of the latter cluster from the first one is proposed. Compared with Re₂(CO)₈[μ-InRe(CO)₅]₂, Re₄(CO)₁₂[μ₃_InRe(CO)₅]₄ shows in polar solvents an unusual high stability, which can be explained by the higher coordination number of In with rhenium carbonyl ligands. Re₄(CO)₁₂-[μ₃-InRe(CO)₅]₄ dissolves monomerically in acetone, where as Re₂(CO)₈[μ-InRe(CO)₅]₂ dissociates yielding Re(CO)₅^? anions. Single-crystal X-ray analyses of Re₄(CO)₁₂[μ₃-InRe(CO)₅]₄ establish the metal skeleton. The central molecular fragment Re₄(CO)₁₂ contains a tetrahedral arrangement of four bonded Re atoms [ReRe 302.8 (5) pm]. The triangles of this fragment are capped with a μ₃-InRe(CO)₅ group each [InRe(terminal) 273.5 (7) pm; InRe (polyhedral) 281.8 (7) pm]. The bridging type of In atoms with the Re₄ tetrahedron and the metal skeleton was realized for the first time. By treating Re₄(CO)₁₂[μ₃-InRe(CO)₅]₄ with Br₂ the existence of Re(CO)₅ ligands could be proved by isolating BrRe(CO)₅.     

Über die Reaktion von Cp2TiCl2 mit [C(NMe2)3][(CO)4FeC(O)NMe2] – Kristallstruktur von [C(NMe2)3]2[FeCl4]

Concerning the Reaction of Cp₂TiCl₂ with [C(NMe₂)₃][(CO)₄FeC(O)NMe₂] – Crystal Structure of [C(NMe₂)₃]₂[FeCl₄] The title compound forms by the reaction of Cp₂TiCl₂ with [C(NMe₂)₃][(CO)₄FeC(O)NMe₂] in THF solution. It crystallizes in the space group Pbcn with a = 1 566.6(3); b = 976.4(2); c = 1 580.4(4) pm; Z = 4; R = 3.8%. Each [FeCl₄]^2? in is surrounded by eight cations. Two cations each are connected with one Cl atom by relatively short H …? Cl contacts leading to a distortion of the tetrahedral geometry of the anion.