Synthese und Struktur von (Ph3PAu)3Mn(CO)4

Synthesis and Structure of (Ph₃PAu)₃Mn(CO)₄ Photolysis of (Ph₃PAu)Mn(CO)₅, Ph₃PAuN₃ and Ph₃PAuNCO yields (Ph₃PAu)₃Mn(CO)₄ ( 1 ). 1 crystallizes in the monoclinic space group P2₁/n with a = 1 031.3(1); b = 3 095.2(3), c = 3 386.3(3) pm; β = 97.58(3)°; Z = 8. The crystal structure contains two symmetry independent clusters 1 of the same geometry. Their inner core MnAu₃ forms a rhombus with distances Mn? Au of about the same lengths between 258.4(4) and 262.0(4) pm. The distances Au? Au range from 276.6(2) to 281.3(2) pm. The bonding in 1 is discussed and compared with those of (Ph₃PAu)₃Co(CO)₃ having the same total number of electrons but a tetrahedral framework.     

Chloroberyllate mit Stickstoff‐Donorliganden. Die Kristallstrukturen von (Ph4P)[BeCl3(Py)], (Ph4P)2[(BeCl3)2(TMEDA)], (Ph4P)[BeCl2{(Me3SiN)2CPh}] und (Ph4P)2[BeCl4] · 2CH2Cl2

Chloroberyllates with Nitrogen Donor Ligands. Crystal Structures of (Ph₄P)[BeCl₃(py)], (Ph₄P)₂[(BeCl₃)₂(tmeda)], (Ph₄P)[BeCl₂{(Me₃SiN)₂CPh}], and (Ph₄P)₂[BeCl₄] · 2CH₂Cl₂ The title compounds were obtained as colourless, moisture sensitive crystals by reactions of (Ph₄P)₂[Be₂Cl₆] with pyridine, tmeda (N, N′‐tetramethylethylendiamine), or with the silylated benzamidine PhC—[N(SiMe₃)₂(NSiMe₃)], whereas the tetrachloro beryllate was isolated as a by‐product from a solution in dichloromethane in the presence of the silylated phosphaneimine Me₃SiNP(tol)₃. All compounds were characterized by crystal structure determinations and by IR spectroscopy. (Ph₄P)[BeCl₃(Py)] ( 1 ): Space group Pbcm, Z = 4, lattice dimensions at 193 K: a = 756.2(1), b = 1739.2(2), c = 2016.3(2) pm, R₁ = 0.0626. The complex anion contains tetrahedrally coordinated beryllium atom with a Be—N distance of 176.5 pm. (Ph₄P)₂[(BeCl₃)₂(tmeda)]·2CH₂Cl₂ ( 2 ·2CH₂Cl₂). Space group P1¯, Z = 1, lattice dimensions at 193 K: a = 1072.7(1), b = 1132.6(1), c = 1248.9(1) pm, α = 95.34(1)°, β = 92.80(1)°, γ = 90.81(1)°, R₁ = 0.0344. Both nitrogen atoms of the tmeda molecule coordinate with BeCl₃^— units forming the centrosymmetric complex anion with Be—N distances of 181.3 pm. (PPh₄)[BeCl₂{(Me₃SiN)₂CPh}] ( 3 ). Space group C2, Z = 2, lattice dimensions at 193 K: a = 1255.4(2), b = 1401.9(2), c = 1085.2(2) pm, R₁ = 0.0288. In the complex anion the benzamidinato ligand {(Me₃SiN)₂CPh}^— acts as chelate with Be—N distances of 174.9 pm. (Ph₄P)₂[BeCl₄]·2CH₂Cl₂ ( 4 ·2CH₂Cl₂). Space group P2/c, Z = 4, lattice dimensions at 193 K: a = 2295.4(1), b = 982.5(1), c = 2197.2(2) pm, β = 99.19(1)°, R₁ = 0.0586. 4 ·2CH₂Cl₂ contains nearly ideal tetrahedral [BeCl₄]^2— ions, like the previously described 4 ·2, 5CH₂Cl₂, which crystallizes in the space group P1¯, with Be—Cl distances of 203.4 pm on average.     

Neue Silber‐Tellurid Cluster stabilisiert mit zweizähnigen Phosphanen: Synthese und Struktur von {[Ag5(TePh)6(Ph2P(CH2)2PPh3)](Ph2P(CH2)2PPh2)}∞, [Ag18Te(TePh)15(Ph2P(CH2)3PPh2)3Cl] und [Ag38Te13(TetBu)12(Ph2P(CH2)2PPh2)3]

Novel Silver‐Telluride Clusters Stabilised with Bidentate Phosphine Ligands: Synthesis and Structure of {[Ag₅(TePh)₆(Ph₂P(CH₂)₂PPh₃)](Ph₂P(CH₂)₂PPh₂)}_∞, [Ag₁₈Te(TePh)₁₅(Ph₂P(CH₂)₃PPh₂)₃Cl], and [Ag₃₈Te₁₃(Te t Bu)₁₂(Ph₂P(CH₂)₂PPh₂)₃] Bidentate phosphine ligands have been found effective to stabilise polynuclear cores containing silver and chalcogenide ligands. They can act as intra and intermolecular bridges between the silver centres. The clusters {[Ag₅(TePh)₆(Ph₂P(CH₂)₂PPh₃)](Ph₂P(CH₂)₂PPh₂)}_∞ ( 1 ), [Ag₁₈Te(TePh)₁₅(Ph₂P(CH₂)₃PPh₂)₃Cl] ( 2 ), and [Ag₃₈Te₁₃(TetBu)₁₂(Ph₂P(CH₂)₂PPh₂)₃] ( 3 ) have been prepared and their molecular structure determined. Compound 2 and 3 are molecular structures with separated cluster cores while 1 forms a polymeric chain bridged by phosphine ligands. ( 1 : space group P2₁/c (No. 14), Z = 4, a = 3518,1(7) pm, b = 2260,6(5) pm, c = 3522,1(7) pm, β = 119,19(3)°; 2 : space group R3 (No. 148), Z = 6, a = b = 3059,4(4) pm, c = 5278,8(9) pm; 3: space group Pccn (No. 56), Z = 4, a = 3613,0(9) pm, b = 3608,6(7) pm, c = 2153,5(8) pm)     

Darstellung und Strukturen von (Et4N)2[Re(CO)3(NCS)3] und (Et4N)[Re(CO)2Br4]

Syntheses and Structures of (Et₄N)₂[Re(CO)₃(NCS)₃] and (Et₄N)[Re(CO)₂Br₄] Rhenium(I) and rhenium(III) carbonyl complexes can easily be prepared by ligand exchange reactions starting from (Et₄N)₂[Re(CO)₃Br₃]. Using nonoxidizing reagents the facial Re^I(CO)₃ unit remains and only the bromo ligands are exchanged. Following this procedure, (Et₄N)₂[Re(CO)₃(NCS)₃] can be obtained in high yield and purity using trimethylsilylisothiocyanate. The compound crystallizes in the monoclinic space group P2₁/n, a = 18.442(5), b = 17.724(3), c = 18.668(5) Å, β = 92.54(1)°, Z = 8. The NCS^? ligands are coordinated via nitrogen. The reaction of [Re(CO)₃Br₃]^2? with Br₂ yields the rhenium(III) anion [Re(CO)₂Br₄]^?. The tetraethylammonium salt of this complex crystallizes in the noncentrosymmetric, orthorhombic space group Cmc2₁, a = 8.311(1), b = 25.480(6), c = 8.624(1) Å, Z = 4. The carbonyl ligands are positioned in a cis arrangement. Their strong trans influence causes a lengthening of the Re? Br bond distances by at least 0.05 Å.     

Darstellung und Kristallstrukturen von (Ph3PNPPh3)2[Re2Br10] und (Ph4P)[Re2Br9]

Synthesis and Crystal Structures of (Ph₃PNPPh₃)₂[Re₂Br₁₀] and (Ph₄P)[Re₂Br₉] Depending on the molar ratio by reaction of [n-Bu₄N]₂[ReBr₆] with the Lewis acid BBr₃ in dichloromethane the bioctahedral complexes [n-Bu₄N]₂[Re₂Br₁₀] and [n-Bu₄N][Re₂Br₉] are formed. The X-ray structure determination on (Ph₃PNPPh₃)₂[Re₂Br₁₀] (monoclinic, space group C 2/c, a = 20.007(4), b = 15.456(5), c = 24.695(4) Å, β = 107.53(2)°, Z = 4) reveals a centrosymmetric edge-sharing complex anion with approximate D_2h symmetry and mean terminal and bridging Re–Br bond lengths of 2.453 (equatorial), 2.482 (axial) and 2.591 Å, respectively, and a Re–Re distance of 3.880 Å. (Ph₄P)[Re₂Br₉] (triclinic, space group P 1, a = 11.062(2), b = 12.430(3), c = 13.163(5) Å, α = 72.94(2), β = 68.47(2), γ = 82.09(2)°, Z = 2) contains a confacial bioctahedral anion with nearly D_3h symmetry and mean terminal and bridging Re–Br distances of 2.460 and 2.536 Å, respectively, and a Re–Re distance of 2.780 Å.     

Darstellung,Strukturen und Eigenschaften von Tris-hexamethyl-trisila-tetraphospha-nortricyclen-bis-chromtricarbonyl [P4(Sime2)3]3[Cr(CO)3]2

Preparation, Structures, and Properties of Tris-hexamethyl-trisila-tetraphospha-nortricyclene-bis-chromiumtricarbonyl [P₄(Sime₂)₃]₃[Cr(CO)₃]₂ Hexamethyl-trisila-tetraphospha-nortricyclene P₄(Sime₂)₃ 1 reacts with C₆H₆Cr(CO)₃ or (CHT)Cr(CO)₃ (CHT ? Cycloheptatriene) under formation of [P₄(Sime₂)₃]₃[Cr(CO)₃]₂ 3 (red crystals), in which each of the Cr atoms is attached to one P atom of a P₃ ring of the three molecules 1 . 3 can also be prepared by heating a solution of P₄(Sime₂)₃Cr(CO)₅ in benzene or THF up to 120–1307deg;C. The compound 3 crystallizes in an orthorhombic and a hexagonal form, the latter being stabilized by one mole toluene. As revealed by single crystal investigations, the symmetry ¯6, distances and angles are nearly unchanged. The o-form corresponds to a face centered cubic packing of the molecules, whereas the h-form is hexagonal close packed.     

Tellurium-bridged manganese carbonyl clusters: synthesis and structural transformations of [Te4Mn3(CO10]-, [Te2Mn3(CO)9]2-, [Te2Mn3(CO)9]-, and [Te2Mn4(CO)12]2-

The reactions of appropriate ratios of K2TeO3 and [Mn2(CO)10)] in superheated methanol solutions lead to a series of novel cluster anions [Te4Mn3(CO)10] (1), [Te2Mn3(CO)9]2- (2), [Te2Mn3(CO)9]- (3), and [Te2Mn4(CO)12]2- (4). When cluster 1 is treated with [Mn2(CO)10]/KOH in methanol, paramagnetic cluster 2 is formed in moderate yield. Cluster 2 is oxidized by [Cu(MeCN)4]BF4 to give the closo-cluster [Te2Mn3(CO)9]- (3), while treatment of 2 with [Mn2(CO)10]/KOH affords the closo-cluster 4. IR spectroscopy showed that cluster 1 reacted with [Mn2(CO)10] to give cluster 4 via cluster 2. Clusters 1-4 were structurally characterized by spectroscopic methods or/and X-ray analyses. The core structure of 1 can be described as two [Mn(CO)3] groups doubly bridged by two Te2 fragments in a mu2-eta2 fashion. Both [Mn(CO)3] groups are further coordinated to one [Mn(CO)4] moiety. Cluster 2 is a 49 e- species with a square-pyramidal core geometry. While cluster 3 displays a trigonal-bipyramidal metal core, cluster 4 possesses an octahedral core geometry.     

Synthese,Schwingungsspektren und Kristallstrukturen der Nitratoargentate (Ph4P)[Ag(NO3)2(CH3CN)]·CH3CN und (Ph4P)[Ag2(NO3)3]

Synthesis, Vibrational Spectra, and Crystal Structures of the Nitrato Argentates (Ph₄P)[Ag(NO₃)₂(CH₃CN)]·CH₃CN and (Ph₄P)[Ag₂(NO₃)₃] Tetraphenylphosphonium bromide reacts in acetonitril suspension with excess silver nitrate to give (Ph₄P)[Ag(NO₃)₂(CH₃CN)]·CH₃CN ( 1 ), whereas (Ph₄P)[Ag₂(NO₃)₃] ( 2 ) is obtained in a long‐time reaction from (Ph₄P)Br and excess AgNO₃ in dichloromethane suspension. Both complexes were characterized by vibrational spectroscopy (IR, Raman) and by single crystal structure determinations. 1 : Space group P2₁/c, Z = 4, lattice dimensions at 193 K: a = 1781.5(3), b = 724.8(1), c = 2224.2(3) pm, β = 96.83(1)°, R₁ = 0.0348. 1 contains isolated complex units [Ag(NO₃)₂(CH₃CN)]^?, in which the silver atom is coordinated by the chelating nitrate groups and by the nitrogen atom of the solvated CH₃CN molecule with a short Ag—N distance of 220.7(4) pm. 2 : Space group I2, Z = 4, lattice dimensions at 193 K: a = 1753.4(4), b = 701.7(1), c = 2105.5(4) pm, R₁ = 0.072. In the polymeric anions [Ag₂(NO₃)₃]^? each silver atom is coordinated in a chelating manner by one nitrate group and by two oxygen atoms of two bridging nitrate ions. In addition, each silver atom forms a weak π‐bonding contact with a phenyl group of the (Ph₄P)⁺ ions with shortest Ag···C separations of 266 and 299 pm, respectively, indicating a (4+1) coordination of silver atoms.     

Iodoplumbate mit polymeren Anionen – Synthese und Kristallstrukturen von [Na3(OCMe2)12][Pb4I11(OCMe2)], (Ph4P)2[Pb5I12] und (Ph4P)4[Pb15I34(dmf)6]

Iodoplumbates with Polymeric Anions – Synthesis and Crystal Structures of [Na₃(OCMe₂)₁₂][Pb₄I₁₁(OCMe₂)], (Ph₄P)₂[Pb₅I₁₂], and (Ph₄P)₄[Pb₁₅I₃₄(dmf)₆] Reactions of PbI₂ with NaI in polar organic solvents followed by crystallization with large cations yield iodoplumbate complexes with various compositions and structures. [Na₃(OCMe₂)₁₂][Pb₄I₁₁(OCMe₂)] 3 , (Ph₄P)₂[Pb₅I₁₂] 4 and (Ph₄P)₄[Pb₁₅I₃₄(dmf)₆] 7 contain one-dimensional infinite anionic chains of face- or edge-sharing PbI₆ or PbI₅L (L = acetone, DMF) octahedra. [Na₃(OCMe₂)₁₂][Pb₄I₁₁(OCMe₂)] 3 : Space group P1 (No. 1), a = 1120.3(5), b = 1265.3(6), c = 1608.3(8) pm, α = 74.64(4), β = 70.40(4), γ = 85.24(4)°, V = 2071(2) · 10⁶ pm³; (Ph₄P)₂[Pb₅I₁₂] 4 : Space group C2/c (No. 15), a = 787.00(10), b = 2812.0(5), c = 3115.9(5) pm, β = 96.240(13)°, V = 6885(2) · 10⁶ pm³; (Ph₄P)₄[Pb₁₅I₃₄(dmf)₆] 7 : Space group P2₁/n (No. 14), a = 2278.8(4), b = 1782.6(3), c = 2616.8(4) pm, β = 114.432(13)°, V = 9678(3) · 10⁶ pm³.     

Synthese und Eigenschaften von Ph3Sn‐substituierten Telluraten – Die Kristallstrukturen von trans‐[(Ph3SnO)4Te(OH)2] und trans‐[(Ph3SnO)2Te(OMe)4]

The reaction of Te(OH)₆ with Ph₃SnOH in ethanol leads to the formation of trans‐[(Ph₃SnO)₄Te(OH)₂] ( 1 ). Compound 1 crystallizes triclinic in the space group P\bar{1} with a = 996.6(2) pm, b = 1365.4(3) pm, c = 1368.2(3) pm and α = 71.15(2)°, β = 71.48(2)°, γ = 74.81(3)° (at 220 K). The molecular structure of 1 consists of a tellurium atom, which is coordinated nearly octahedrally by four Ph₃SnO units and two hydroxyl groups that are trans to each other. The Te–O bond lengths are in the range of 190.5(2) and 193.7(2) pm. Treatment of 1 with methanol under reflux yields trans‐[(Ph₃SnO)₂Te(OMe)₄] ( 2 ). Compound 2 crystallizes triclinic in the space group P\bar{1} with a = 1012.8(1) pm, b = 1422.4(2) pm, c = 1618.1(2) pm, and α = 100.44(1)°, β = 107.92(1)°, γ = 110.66(1)° (at 220 K). 2 forms centrosymmetric molecules in which the tellurium atom is surrounded nearly octahedrally by four methoxy groups and two trans arranged Ph₃SnO units. The Te–O bond lengths of 187.9(3)–194.5(3) pm are similar to those observed in 1 .     

Synthese und Strukturen von [ReNBr2(Me2PhP)3] und (Me2PhPH)[fac‐Re(NBBr3)Br3(Me2PhP)2]

Syntheses and Structures of [ReNBr₂(Me₂PhP)₃] and (Me₂PhPH)[ fac ‐Re(NBBr₃)Br₃(Me₂PhP)₂] [ReNBr₂(Me₂PhP)₃] ( 1 ) has been prepared by the reaction of [ReNCl₂(Me₂PhP)₃] with Me₃SiBr in dichloromethane. The bromo complex reacts with BBr₃ under formation of [Re(NBBr₃)Br₂(Me₂PhP)₃] ( 2 ) or (Me₂PhPH)[fac‐Re(NBBr₃)Br₃(Me₂PhP)₂] ( 3 ) depending on the experimental conditions. The formation of the nitrido bridge leads to a significant decrease of the structural trans influence of the nitrido ligand which is evident by the shortening of the Re‐(trans)Br bond from 2.795(1) Å in [ReNBr₂(Me₂PhP)₃] to 2.620(1) Å in [fac‐Re(NBBr₃)Br₃(Me₂PhP)₂]^– and 2.598(1) Å in [Re(NBBr₃)Br₂(Me₂PhP)₃], respectively.     

Synthese,Kristallstruktur und spektroskopische Charakterisierung von [Au12(PPh)2(P2Ph2)2(dppm)4Cl2]Cl2

Synthesis, Crystal Structure and Spectroscopic Characterization of [Au₁₂(PPh)₂(P₂Ph₂)₂(dppm)₄Cl₂]Cl₂ The reaction of [(AuCl)₂dppm] (dppm = Ph₂PCH₂PPh₂) with P(Ph)(SiMe₃)₂ in CHCl₃ results in the formation of [Au₁₂(PPh)₂(P₂Ph₂)₂(dppm)₄Cl₂]Cl₂ ( 1 ), the crystal structure of which was determined by single crystal X‐ray analysis (space group P2₁/c, a = 1425.3(3) pm, b = 2803.7(6) pm, c = 2255.0(5) pm, β = 95.00(3)°, V = 8977(3)·10⁶ pm³, Z = 2). The dication in 1 consists of two Au₆P₃ units built by highly distorted Au₃P and Au₂P₂ heterotetrahedra, connected via four bidentate phosphine ligands. Additionally, the compound was characterized by IR‐, UV‐ and NMR spectroscopy. The ³¹P{¹H} NMR spectrum is discussed in detail.     

Synthese und Kristallstrukturen von (PPh4)2[TeS3] · 2 CH3CN und (PPh4)2[Te(S5)2]

Synthesis and Crystal Structures of (PPh₄)₂[TeS₃] · 2 CH₃CN and (PPh₄)₂[Te(S₅)₂] (PPh₄)₂[TeS₃] · 2 CH₃CN was obtained by the reaction of PPh₄Cl, Na₂S₄ and Te in acetonitrile. With sulfur it reacts yielding (PPh₄)₂[Te(S₅)₂]. The crystal structures of both products were determined by X-ray diffraction. (PPh₄)₂[TeS₃] · 2 CH₃CN: triclinic, space group P1 , Z = 2, R = 0.041 for 4 629 reflexions; it contains trigonal-pyramidal [TeS₃]^2? ions with an average Te? S bond length of 233 pm. (PPh₃)₂[Te(S₅)₂]: monoclinic, P2₁/n, Z = 2, R = 0.037 for 2 341 reflexions. In the [Te(S₅)₂]^2? ion the tellurium atom has a nearly square coordination by four S atoms. Along with the Te atoms each of the two S₅ groups forms a ring with chair conformation.