[Cu12(NPEt3)8]4+ and [Ag12(NPEt3)8]4+: Cubane Structures

Unusual, highly symmetrical cubes are formed by the dodecameric cationic phosphoraneiminato complexes of copper(I ) and silver(I ) [M₁₂(NPEt₃)₈]⁴⁺, in which the metal atoms occupy the edges and the N atoms of NPEt ³⁻₃ groups the corners of the cube (see figure). The structures can be understood as molecular sections of the Cu₃N structure, which is inverse to the ReO₃‐type structure.     

[Ag12F(NPEt3)8]3+: Ein durch Fluorid gefüllter Metalla‐Cryptand

[Ag₁₂F(NPEt₃)₈]³⁺: A Metalla‐Cryptand filled with a Fluoride Ion [Ag₁₂F(NPEt₃)₈](SiF₆)_1,5 ( 1 ) was obtained from the reaction of silver(I) fluoride with the silylated phosphaneimine Me₃SiNPEt₃ in acetonitrile. It forms colorless, light‐ and hydrolysis‐sensitive crystals, which incorporate acetonitrile that is lost in vacuo. 1 · 2,4 CH₃CN was characterized by its IR spectrum and by X‐ray crystal structure analysis. Space group Pa 3, Z = 8, a = 2734.8(1) pm at 153 K, R = 0.059. The compound consists of cations [Ag₁₂F(NPEt₃)₈]³⁺ (point group C₃), SiF₆^2– counter‐ions and acetonitrile molecules which show no interactions. In the cation the silver atoms are located on the edges of a nearly undistorted cube and the N atoms of the phosphoraneiminato groups (NPEt₃^–) occupy the vertices. A fluoride ion in the center of the cube has contacts of nearly similar length to the 12 silver atoms (mean distance 304.7 pm).     

Synthese und Kristallstrukturen der Phosphaniminato-Komplexe [SbF2(NPEt3)]2 und [SbF(NPEt3)2]2 sowie von NMe4+SbF4−

Synthesis and Crystal Structures of the Phosphoraneiminato Complexes [SbF₂(NPEt₃)]₂ and [SbF(NPEt₃)₂]₂ as well as of NMe₄⁺SbF₄^? The title compounds have been prepared from antimony trifluoride with the silylated phosphaneimine Me₃SiNPEt₃ and [NMe₄]F, respectively. They were characterized by IR spectroscopy and by crystal structure determinations. [SbF₂(NPEt₃)]₂ : Space group Pbca, Z = 8, structure determination with 1264 unique reflections, R₁ = 0.028 for reflections with I > 2σ(I). Lattice dimensions at ?80°C: a = 1284.8, b = 1162.4, c = 1380.4 pm. The compound forms centrosymmetric dimeric molecules, in which the Ψ-trigonal-bipyramidal coordinated antimony atoms are linked via μ₂-N bridges of the NPEt₃^? ligands. [SbF(NPEt₃)₂]₂ : Space group P2₁/c, Z = 4, structure determination with 2270 unique reflections, R₁ = 0.029 for reflections with I > 2μ(I). Lattice dimensions at ?75°C: a = 815.8, b = 1121.2, c = 2068.5 pm, β = 101.09°. The compound forms centrosymmetric dimeric molecules, in which the Ψ-trigonal-bipyramidal coordinated antimony atoms are linked via μ₂-N bridges of one of the two NPEt₃^? ligands. The other NPEt₃^? group is terminally connected. NMe₄⁺SbF₄^? : Space group P2₁/c, Z = 4, structure determination with 1503 unique reflections, R₁ = 0.069 for reflections with I > 2μ(I). Lattice dimensions at ?50°C: a = 539.80, b = 896.10, c = 1760.3 pm, β = 90.338°. The compound includes monomeric SbF₄^? ions with distorted Ψ-trigonal-bipyramidal environment of the antimony atoms.     

Phosphaniminato-Komplexe von Titan(IV). Die Kristallstrukturen von [TiCl3(NPEt3)]2, [TiCl3(NPEt3)(THF)2] und [TiCl4{Me2Si(NPEt3)2}]

Phosphoraneiminato Complexes of Titanium(IV). Crystal Structures of [TiCl₃(NPEt₃)]₂, [TiCl₃(NPEt₃)(THF)₂], and [TiCl₄{Me₂Si(NPEt₃)₂}] [TiCl₃(NPEt₃)]₂ ( 1 ) is formed from titanium(IV) chloride and the silylated phosphaneimine Me₃SiNPEt₃ in dichloromethane as reddish-brown, moisture-sensitive crystals. According to the crystal structure analysis these crystals show centrosymmetric Ti₂N₂ four-membered rings with Ti–N distances of 184.7 and 210.3 pm. With tetrahydrofurane 1 forms yellow, moisture sensitive crystals of the solvate [TiCl₃(NPEt₃)(THF)₂] ( 2 ), in which the titanium atom is octahedrally coordinated. The THF molecule which is in trans position to the phosporaneiminato ligand realizes but a very weak Ti–O bond of 238.0 pm, the cis THF molecule shows a Ti–O distance of 213.7 pm. With 173.4 pm along with a TiNP bond angle of 160.0° the TiN distance is very short. The bis(phosphaneimine) complex [TiCl₄{Me₂Si(NPEt₃)₂}] ( 3 ) is formed as colourless crystals in low yield in the reaction of titanium(IV) chloride with Me₃SiNPEt₃ and trimethylcyclopentadienylsilane. In 3 the titanium atom is surrounded by four chlorine atoms in a distorted octahedral fashion and by the two N atoms of the Me₂Si(NPEt₃)₂ molecule with TiN distances of 205.6 pm.     

[(HBNPEt3)4NPEt3]3+ – ein bicyclisches Penta(phosphorano)boraziniumTrikation

[(HBNPEt₃)₄NPEt₃]³⁺ – a Bicyclic Penta(phosphorano)borazinium Trication [(HBNPEt₃)₄NPEt₃]Br₃ ( 1 ) has been prepared by the reaction of Me₃SiNPEt₃ with [HBBr₂(SMe₂)] in dichloromethane solution at 20°C. According to ¹¹B‐NMR and ³¹P‐NMR spectroscopy and to a crystal structure determination the cation of 1 has the structure of a bicyclic penta(phosphorano)borazinium‐trication. 1 _.3CH₂Cl₂: Space group P2₁2₁2₁, Z = 8, lattice dimensions at –83°C: a = 2124.8(1), b = 2307.6(1), c = 2323,1(1) pm, R₁ = 0.0733.     

Phosphaniminato‐Acetato‐Cluster von Kupfer und Zink. Kristallstrukturen von [Cu4(NPEt3)2(O2CCH3)6] und [Zn4(NPEt3)2(O2CCH3)6]

Phosphoraneiminato Acetate Cluster of Copper and Zinc. Crystal Structures of [Cu₄(NPEt₃)₂(O₂CCH₃)₆] and [Zn₄(NPEt₃)₂(O₂CCH₃)₆] The anhydrous acetates of copper(II) and zinc react with the silylated phosphaneimine Me₃SiNPEt₃ in dichloromethane at 20 °C forming the mixed phosphoraneiminato acetate clusters [Cu₄(NPEt₃)₂(O₂CCH₃)₆] ( 1 ), which forms emerald crystals, and colourless [Zn₄(NPEt₃)₂ · (O₂CCH₃)₆] ( 2 ). In spite of analogous composition the structures of 1 and 2 are completely different. In the asymmetric unit of 1 three copper atoms of an almost isosceles triangle are linked via two nitrogen atoms of the NPEt₃^– groups to form a trigonal bipyramidal aggregate. One of these three copper atoms is chelated by an acetate group, another one is connected with the fourth copper atom via three μ₂‐O₂C–CH₃ groups. The asymmetric units are associated via a μ₂‐O₂C–CH₃ group and a μ₃‐OC(O)CH₃ group at a time so that infinite chains result. In 2 two zinc atoms are linked via the nitrogen atoms of the two NPEt₃^– groups to form an almost centrosymmetric four‐membered ring. Both nitrogen atoms of the four‐membered ring are connected with another zinc atom each. These zinc atoms again are linked with the zinc atoms of the Zn₂N₂ four‐membered ring via two μ₂‐O₂C–CH₃ groups each and additionally coordinated with a terminal acetate ligand each.     

Cubane Tellurido Clusters [Zn(NH3)4]3[Mo4Te4(CN)12] and [Cd(NH3)4]3[W4Te4(CN)12]: Syntheses and Crystal Structures

Single crystals of [Zn(NH₃)₄]₃[Mo₄Te₄(CN)₁₂] (I) and [Cd(NH₃)₄]₃[W₄Te₄(CN)₁₂] (II) were obtained by applying solutions of K₇[Mo₄Te₄(CN)₁₂] · 11H₂O and K₆[W₄Te₄(CN)₁₂] · 5H₂O in aqueous ammonia over solutions of ZnCl₂ and Cd(NO₃)₂ in glycerol and were characterized by X-ray diffraction analysis. The IR spectra and thermal properties of compounds I and II were examined.     

Phosphaniminato‐Cluster von Eisen. Die Kristallstrukturen von [FeCl(NPEt3)]4, [Fe(C=C–SiMe3)(NPEt3)]4 und [Fe3Cl4{NP(NMe2)3}3]

Phosphoraneiminato Cluster of Iron. The Crystal Structures of [FeCl(NPEt₃)]₄, [Fe(C=C–SiMe₃)(NPEt₃)]₄, and [Fe₃Cl₄{NP(NMe₂)₃}₃] The reaction of iron dichloride with the silylated phosphaneimine Me₃SiNPEt₃ in the presence of potassium fluoride at 165 ?C leads to the phosphoraneiminato complex [FeCl(NPEt₃)]₄ ( 1 ). Compound 1 forms black, moisture and oxygen sensitive crystals. According to the crystal structure analysis 1 has a heterocubane structure, in which the iron and the nitrogen atoms of the NPEt₃^– groups occupy the corners of a distorted cube and form Fe–N–Fe bond angles of 83.1? and N–Fe–N angles of 96.5?. This results in significantly short Fe…Fe contacts of 272.9 pm. The results of magnetic susceptibility measurements in the range of temperatures from 1.8 to 293 K and the ⁵⁷Fe‐Mössbauer spectra in the range of temperatures from 2 to 300 K are reported. Compound 1 reacts with the lithiated acetylenes LiC=C–CMe₃ and LiC=C–SiMe₃ in n‐hexane to form the iron‐organic derivatives [Fe(C=C–R)(NPEt₃)]₄ [R = CMe₃ ( 2 a ), R = SiMe₃ ( 2 b )] keeping the heterocubane structure. Compounds 2 a and 2 b form crystals which are very reactive and also black. According to the crystal structure analysis 2 b has a Fe₄N₄ heterocubane structure which is less distorted than that in 1 with bond angles Fe–N–Fe of 85.5? and N–Fe–N of 94.2?. This leads to the longer Fe…Fe contacts of 281.4 pm. With the dimethylamido derivative Me₃SiNP(NMe₂)₃ iron dichloride reacts under conditions similar to those in the synthesis of 1 to form the dark green mixed‐valenced Fe^II/Fe^III cluster [Fe₃Cl₄{NP(NMe₂)₃}₃] ( 3 ). According to the crystal structure analysis the three iron atoms in 3 are connected via one μ₃‐N atom of a NP(NMe₂)₃^– ligand, via two μ‐N atoms of the two remaining phosphoraneiminato ligands, and via one μ‐Cl atom to form an incomplete heterocubane skeleton.     

Fluorination of [Os3(CO)12] and [Ir4(CO)12

Fluorination of [Os(3)CO(12)] in HF/SbF(5) affords [Os(CO)(4)(FSbF(5))(2)]. According to its crystal structure (orthorhombic, Pna2(1), a = 1590.3(3), b = 1036.6(1), c = 878.2(2) pm, Z = 4), the two SbF(6) units occupy cis positions in the octahedral environment around the Os atom. Fluorination of [Ir(4)(CO)(12)] in HF/SbF(5) produced three different compounds: (1) [Ir(4)(CO)(8)(mu-F)(2)(Sb(2)F(11))(2)] (tetragonal, P4n2, a = 1285.2(2), c = 952.9(1) pm, Z = 2). Here, two of the six edges of the Ir(4) tetrahedron in [Ir(4)CO(12)] are replaced by bridging fluorine atoms. (2) [fac-Ir(CO)(3)(FSbF(5))(2)HF]SbF(6).HF (orthorhombic, Pnma, a = 1250.6(1), b = 1340.7(2), c = 1092.6(2) ppm, Z = 4). The Ir(4) tetrahedron in Ir(4)(CO)(12) is completely broken down, but the facial Ir(CO)(3) configuration is retained. (3) [mer-Ir(CO)(3)F(FSbF(5))(2)] (triclinic, P1, a = 834.9(1), b = 86 4.9(1), c = 1060.0(1) pm, alpha = 69.173(4) degrees, beta = 77.139(4) degrees, gamma = 88.856(4) degrees, Z = 2).     

Phosphaniminato-Komplexe von Bor. Synthese und Kristallstrukturen von [BBr2(NPMe3)]2, [B2Br3(NPiPr3)2]Br, [B2(NPEt3)4]Br2, [B2Br2(NPPh3)3]BBr4 und [{B2(NMe2)2}2(NPEt3)2]Cl2

Phosphoraneiminato Complexes of Boron. Syntheses and Crystal Structures of [BBr₂(NPMe₃)]₂, [B₂Br₃(NPⁱPr₃)₂]Br, [B₂(NPEt₃)₄]Br₂, [B₂Br₂(NPPh₃)₃]BBr₄ and [{B₂(NMe₂)₂}₂(NPEt₃)₂]Cl The bromoderivatives of the title compounds are prepared from the corresponding silylated phosphoraneimines Me₃SiNPR₃ and boron tribromide. The boron subcompound [{B₂(NMe₂)₂}₂(NPEt₃)₂]Cl₂ derives from Me₃SiNPEt₃ and B₂Cl₂(NMe₂)₂. All complexes are characterized by NMR and IR spectroscopy as well as by crystal structure determinations. [BBr₂(NPMe₃)]₂ (1): Space group P2₁/n, Z = 2, R = 0.031. Lattice dimensions at ?50°C: a = 723.8, b = 894.2, c = 1305.4 pm, β = 92.35°. 1 forms centrosymmetric molecules in which the boron atoms are linked via μ₂-N bridges of the NPMe₃^? groups of from B₂N₂ four-membered rings with B? N distances of 149.9 and 150.9 pm. B₂Br₃(NPⁱPr₃)₂]Br (2): Space group P2₁, Z = 2, R = 0.059. Lattice dimensions at ?80°C: a = 817.6, b = 2198.7, c = 851.5 pm, β = 115.09°. In the cations of 2 the boron atoms are lined via the μ₂-N atoms of the NPⁱPr₃^? groups to form planar, asymmetric B₂N₂ four-membered rings with B? N distances of 143 and 156 pm. [B₂(NPEt₃)₄[Br₂·4CH₂Cl₂ (3): Space group C2/c, Z = 4, R = 0.042. Lattice dimensions at ?50°C: a = 1946.1, b = 1180.3, c = 2311.3 pm, β = 101.02°. The structure contains centrosymmetric dications in which both the boron atoms are lined by the N atoms of two of the NPEt₃^? groups to form a B₂N₂ four-membered ring with B? N distances of 149.6 pm. The remaining two NPEt₃^? groups are terminally bonded with very short B? N distances of 133.5 pm. B₂Br₂(NPPh₃)₃]BBr₄ (4): Space group P1 , Z = 2, R = 0.065. Lattice dimension at ?50°C: a = 1025.7, b = 1496.1, c = 1807.0 pm, α = 85.09°, β = 82.90°, γ = 82.72°. In the cation the boron atoms are lined via the μ₂-N atoms of two of the NPPh₃^? groups to form a nearly planer B₂N₂ four-membered ring with B? N distances of 149.3-153.1 pm. The third NPPh₃³ group is terminally connected with teh sp² hybridized boron atom and with a B? N distance of 134.1 pm along with an almost linear BNP bond angle of 173.6°. [{B₂(NMe₂)₂}₂(NPEt₂)₂]Cl₂ · 3CH₂Cl₂ (5): Space group C2/c, Z = 4, R = 0.098. Lattice dimensions at ?70°C: a = 1557.9, b = 1294.7, c = 2122.9 pm, β = 96.08°. The structure of 4 contains centrosymmetric dications in which two by two B-B dumb-bells are linked via the μ₂-N atoms of the two NEPt₃^? groups to form B₄N₂ six-membered rings with B? N distances of 150 and 156 pm and B-B distances of 173 pm. The B? N distances of the terminally bonded NMe₂^? groups correspond to 138 pm double bonds.     

Drei neue Selenoborato-closo-dodekaborate: Synthesen und Kristallstrukturen von Rb8[B12(BSe3)6], Rb4Hg2[B12(BSe3)6] und Cs4Hg2[B12(BSe3)6]

Three Novel Selenoborato- closo -dodecaborates: Syntheses and Crystal Structures of Rb₈[B₁₂(BSe₃)₆], Rb₄Hg₂[B₁₂(BSe₃)₆], and Cs₄Hg₂[B₁₂(BSe₃)₆] The three selenoborates Rb₈[B₁₂(BSe₃)₆] (P1, a = 10.512(5) Å, b = 10.450(3) Å, c = 10.946(4) Å, α = 104.53(3)°, β = 91.16(3)°, γ = 109.11(3)°, Z = 1), Cs₄Hg₂[B₁₂(BSe₃)₆] (P1, a = 9.860(2) Å, b = 10.740(2) Å, c = 11.078(2) Å, α = 99.94(3)°, β = 90.81(3)°, γ = 115.97(3)°, Z = 1), and Rb₄Hg₂[B₁₂(BSe₃)₆] (P1, a = 9.593(2) Å, b = 10.458(2) Å, c = 11.131(2) Å, α = 99.25(3)°, β = 91.16(3)°, γ = 116.30(3)°, Z = 1) were prepared from the metal selenides, amorphous boron and selenium by solid state reactions at 700 °C. These new chalcogenoborates contain B₁₂ icosahedra completely saturated with six trigonal-planar BSe₃ entities functioning as bidentate ligands to form a persubstituted closo-dodecaborate anion. The two isotypic compounds Rb₄Hg₂[B₁₂(BSe₃)₆] and Cs₄Hg₂[B₁₂(BSe₃)₆] are the first selenoborate structures containing a transition metal which are characterized by single crystal diffraction.     

Tetramethylammoniumamalgam, [N(CH3)4]Hg8

Tetramethyl Ammonium Amalgam, [N(CH₃)₄]Hg₈ Crystals of tetramethyl ammonium amalgam with the composition [N(CH₃)₄]Hg₈ were prepared by electrolysis. According to temperature‐dependent X‐ray diffraction experiments the compound transforms into an amorphous product above 6 °C; the decomposition is a multi‐stage process as shown by DTA experiments. X‐ray examinations of crystalline aggregates indicate a structure of low symmetry with remarkable similarities to that of α‐Hg.     

Zinkselenid- und Zinktelluridcluster mit Phenylselenolat- und Phenyltellurolatliganden. Die Kristallstrukturen von [NEt4]2[Zn4Cl4(SePh)6], [NEt4]2[Zn8Cl4Se(SePh)12], [Zn8Se(SePh)14(PnPr3)2], [HPnPr2R]2[Zn8Cl4Te(TePh)12] (R = nPr,Ph) und [Zn10Te4(TePh)12(PR3)2] (R = nPr,Ph)

Zincselenide- and Zinctellurideclusters with Phenylselenolate- and Phenyltellurolateligands. The Crystal Structures of [NEt₄]₂[Zn₄Cl₄(SePh)₆], [NEt₄]₂[Zn₈Cl₄Se(SePh)₁₂], [Zn₈Se(SePh)₁₄(PⁿPr₃)₂], [HPⁿPr₂R]₂[Zn₈Cl₄Te(TePh)₁₂] (R = ⁿPr, Ph), and [Zn₁₀Te₄(TePh)₁₂(PR₃)₂] (R = ⁿPr, Ph) In the prescence of NEt₄Cl ZnCl₂ reacts with PhSeSiMe₃ or a mixture of PhSeSiMe₃/Se(SiMe₃)₂ to form the ionic complexes [NEt₄]₂[Zn₄Cl₄(SePh)₆] 1 or [NEt₄]₂[Zn₈Cl₄Se(SePh)₁₂] 2 respectively. The use of PⁿPr₃ instead of the quarternary ammonia salt leads in toluene to the formation of crystalline [Zn₈Se(SePh)₁₄(PⁿPr₃)₂] 3 . Reactions of ZnCl₂ with PhTeSiMe₃ and tertiary phosphines result in acetone in crystallisation of the ionic clusters [HPⁿPr₂R]₂[Zn₈Cl₄Te(TePh)₁₂] (R = ⁿPr 4 , Ph 5 ) and in THF of the uncharged [Zn₁₀Te₄(TePh)₁₂(PR₃)₂] (R = ⁿPr 6 , Ph 7 ). The structures of 1–7 were obtained by X-ray single crystal structure. ( 1 : space group P2₁/n (No. 14), Z = 4, a = 1212,4(2) pm, b = 3726,1(8) pm, c = 1379,4(3) pm β = 99,83(3)°; 2 space group P2₁/c (Nr. 14), Z = 4, a = 3848,6(8) pm, b = 1784,9(4) pm, c = 3432,0(7) pm, β = 97,78(3)°; 3 : space group Pnn2 (No. 34), Z = 2, a = 2027,8(4) pm, b = 2162,3(4) pm, c = 1668,5(3) pm; 4 : space group P2₁/c (No. 14), Z = 4, a = 1899,8(4) pm, b = 2227,0(5) pm, c = 2939,0(6) pm, β = 101,35(3)°; 5 : space group space group P2₁/n (No. 14), Z = 4, a = 2231,0(5) pm, b = 1919,9(4) pm, c = 3139,5(6) pm, β = 109,97(4)°; 6 : space group I4₁/a (No. 88), Z = 4, a = b = 2566,0(4) pm, c = 2130,1(4) pm; 7 : space group P1¯ (No. 2), Z = 2, a = 2068,4(4) pm, b = 2187,8(4) pm, c = 2351,5(5) pm, α = 70,36°, β = 84,62°, γ( = 63,63°)     

Self-assembly of unprecedented [8+12] Cu-metallamacrocycle-based 3D metal-organic frameworks

[8+12]-metallamacrocycle-based 3D frameworks {[Cu(4)(pbt)(2)(SO(4))(2)(DMF)(2)(CH(3)OH)]·7H(2)O·DMF}(n) (1) and [12]-macrocycle 3D {[Cu(2)(pbt)(SO(4))(DMSO)(CH(3)OH)(2)]·5H(2)O·CH(3)OH}(n) (2) have been obtained. Both complexes display antiferromagnetic couplings and high catalytic activity in the oxidative coupling reaction of 1-ethynylbenzene and oxazolidin-2-one.