(Ph)3PBr][Br7], [(Bz)(Ph)3P]2[Br8], [(n-Bu)3MeN]2[Br20], [C4MPyr]2[Br20], and [(Ph)3PCl]2[Cl2I14]: extending the horizon of polyhalides via synthesis in ionic liquids

The five polyhalides [(Ph)(3)PBr][Br(7)], [(Bz)(Ph)(3)P](2)[Br(8)], [(n-Bu)(3)MeN](2)[Br(20)], [C(4)MPyr](2)[Br(20)] ([C(4)MPyr] = N-butyl-N-methylpyrrolidinium), and [(Ph)(3)PCl](2)[Cl(2)I(14)] were prepared by the reaction of dibromine and iodine monochloride in ionic liquids. The compounds [(Ph)(3)PBr][Br(7)] and [(Bz)(Ph)(3)P](2)[Br(8)] contain discrete pyramidal [Br(7)](-) and Z-shaped [Br(8)](2-) polybromide anions. [(n-Bu)(3)MeN](2)[Br(20)] and [C(4)MPyr](2)[Br(20)] exhibit new infinite two- and three-dimensional polybromide networks and contain the highest percentage of dibromine ever observed in a compound. [(Ph)(3)PCl](2)[Cl(2)I(14)] also consists of a three-dimensional network and is the first example of an infinite polyiodine chloride. All compounds were obtained from ionic liquids as the solvent that, on the one hand, guarantees for a high stability against strongly oxidizing Br(2) and ICl and that, on the other hand, reduces the high volatility of the molecular halogens.     

Synthesis of monohalogeno derivatives of closo-[B9H9]2-. Crystal structures of (Ph4P)2[1-XB9H8].CH3CN (X = Cl, Br, I)

By reaction of Na2[B9H9] with the appropriate N-halogenosuccinimide, the monohalogenated anion [1-XB9H8]2- (X = Cl, Br, or I) is formed. The X-ray diffraction analyses performed on single crystals of (Ph4P)2[1-XB9H8].CH3CN (X = Cl, Br, I) reveal that the tricapped trigonal prismatic geometry of the cluster is retained after substitution in the 1-position. Crystallographic data are as follows for (Ph4P)2[1-XB9H8].CH3CN. X = Cl, Br: monoclinic, space group P2(1), a = 10.7 A, b = 32.9 A, c = 13.8 A, beta = 96 degrees, Z = 4, R1 = 0.038 and R1 = 0.036, respectively. X = I: monoclinic, space group P2(1)/n, a = 10.5 A, b = 13.6 A, c = 33.4 A, beta = 94 degrees, Z = 4, R1 = 0.094. The compounds have been characterized by vibrational and 11B NMR spectroscopy as well.     

Substituted N-picolylethylenediamines of the type (ArNHCH2CH2){(2-C5H4N)CH2}NR [R = Me, 4-CH2=CH(C6H4)CH2, (2-C5H4N)CH2] and their transition metal(II) halide complexes

Alkylation of (ArNHCH2CH2){(2-C5H4N)CH2}NH with RX [RX = MeI, 4-CH2=CH(C6H4)CH2Cl) and (2-C5H5N)CH2Cl] in the presence of base has allowed access to the sterically demanding multidentate nitrogen donor ligands, {(2,4,6-Me3C6H2)NHCH2CH2}{(2-C5H4N)CH2}NMe (L1), {(2,6-Me3C6H3)NHCH2CH2}{(2-C5H4N)CH2}NCH2(C6H4)-4-CH=CH2 (L2) and (ArNHCH2CH2){(2-C5H4N)CH2}2N (Ar = 2,4-Me2C6H3 L3a, 2,6-Me2C6H3 L3b) in moderate yield. L3 can also be prepared in higher yield by the reaction of (NH2CH2CH2){(2-C5H4N)CH2}2N with the corresponding aryl bromide in the presence of base and a palladium(0) catalyst. Treatment of L1 or L2 with MCl2 [MCl2 = CoCl2.6H2O or FeCl2(THF)1.5] in THF affords the high spin complexes [(L1)MCl2](M = Co 1a, Fe 1b) and [(L2)MCl2](M = Co 2a, Fe 2b) in good yield, respectively; the molecular structure of reveals a five-coordinate metal centre with bound in a facial fashion. The six-coordinate complexes, [(L3a)MCl2](M = Co 3a, Fe 3b, Mn 3c) are accessible on treatment of tripodal L3a with MCl2. In contrast, the reaction with the more sterically encumbered leads to the pseudo-five-coordinate species [(L3b)MCl2](M = Co 4a, Fe 4b) and, in the case of manganese, dimeric [(L3b)MnCl(mu-Cl)]2 (4c); in 4a and 4b the aryl-substituted amine arm forms a partial interaction with the metal centre while in 4c the arm is pendant. The single crystal X-ray structures of , 1a, 3b.MeCN, 3c.MeCN, 4b.MeCN and 4c are described as are the solution state properties of 3b and 4b.     

Triazenide-bridged rhodium-palladium complexes: [I2Rh(mu-p-MeC6H4NNNC6H4Me-p)2Pd(eta(3)-C3H5)]-, a stable paramagnetic [RhPd]4+ species with a localised Rh(II) centre

Deprotonation of mixtures of the triazene complexes [RhCl(CO)2(p-MeC6H4NNNHC6H4Me-p)] and [PdCl(eta(3)-C3H5)(p-MeC6H4NNNHC6H4Me-p)] or [PdCl2(PPh3)(p-MeC6H4NNNHC6H4Me-p)] with NEt3 gives the structurally characterised heterobinuclear triazenide-bridged species [(OC)2Rh(mu-p-MeC6H4NNNC6H4Me-p)2PdLL'] {LL' = eta(3)-C3H5 1 or Cl(PPh3) 2} which, in the presence of Me3NO, react with [NBu(n)4]I, [NBu(n)4]Br, [PPN]Cl or [NBu(n)4]NCS to give [(OC)XRh(mu-p-MeC6H4NNNC6H4Me-p)2PdCl(PPh3)]- (X = I 3-, Br 4-, Cl 5- or NCS 6-) and [NBu(n)4][(OC)XRh(mu-p-MeC6H4NNNC6H4Me-p)2Pd(eta(3)-C3H5)], (X = I 7- or Br 8-). The allyl complexes 7- and 8- undergo one-electron oxidation to the corresponding unstable neutral complexes 7 and 8 but, in the presence of the appropriate halide, oxidative substitution results in the stable paramagnetic complexes [NBu(n)4][X2Rh(mu-p-MeC6H4NNNC6H4Me-p)2Pd(eta(3)-C3H5)], (X = I 9- or Br 10-). X-Ray structural (9-), DFT and EPR spectroscopic studies are consistent with the unpaired electron of 9- and 10- localised primarily on the Rh(II) centre of the [RhPd]4+ core, which is susceptible to oxygen coordination at low temperature to give Rh(III)-bound superoxide.     

Haloacyl complexes of boron, [(CF3)3BC(O)Hal]- (Hal=F, Cl, Br, I)

The haloacyltris(trifluoromethyl)borate anions [(CF3)3BC(O)Hal]- (Hal=F, Cl, Br, I) have been synthesized by reacting (CF3)3BCO with either MHal (M=K, Cs; Hal=F) in SO2 or MHal (M=[nBu4N]+, [Et4N]+, [Ph4P]+; Hal=Cl, Br, I) in dichloromethane. Metathesis reactions of the fluoroacyl complex with Me3SiHal (Hal=Cl, Br, I) led to the formation of its higher homologues. The thermal stabilities of the haloacyltris(trifluoromethyl)borates decrease from the fluorine to the iodine derivative. The chemical reactivities decrease in the same order as demonstrated by a series of selected reactions. The new [(CF3)3BC(O)Hal]- (Hal=F, Cl, Br) salts are used as starting materials in the syntheses of novel compounds that contain the (CF3)3B-C fragment. All borate anions [(CF3)3BC(O)Hal]- (Hal=F, Cl, Br, I) have been characterized by multinuclear NMR spectroscopy (11B, 13C, 17O, 19F) and vibrational spectroscopy. [PPh4][(CF3)3BC(O)Br] crystallizes in the monoclinic space group P2/c (no. 13) and the bond parameters are compared with those of (CF3)3BCO and K[(CF3)3BC(O)F]. The interpretation of the spectroscopic and structural data are supported by DFT calculations [B3LYP/6-311+G(d)].     

Influence of hydrogen bonding on the assembly of six-membered vanadium borophosphate cluster anions: synthesis and structures of (NH4)2(C2H10N2)6[Sr(H2O)5]2[V2P2BO12](6)10H2O, (NH4)2(C3H12N2)6[Sr(H2O)4]2[V2P2BO12](6)17H2O, and (NH4)3(C4H14N2)4 5[Sr(H2O)5]2[Sr(H2O)4][V2P2BO12]6 10H2O

Three new strontium vanadium borophosphate compounds, (NH4)2(C2H10N2)6[Sr(H2O)5]2[V2P2BO12]6 10H2O (Sr-VBPO1) (1), (NH4)2(C3H12N2)6[Sr(H2O)4]2[V2P2BO12]6 17H2O (Sr-VBPO2) (2), and (NH4)3(C4H14N2)4.5[Sr(H2O)5]2[Sr(H2O)4][V2P2BO12]6 10H2O (Sr-VBPO3) (3) have been synthesized by interdiffusion methods in the presence of diprotonated ethylenediamine, 1,3-diaminopropane, and 1,4-diaminobutane. Compound 1 has a chain structure, whereas 2 and 3 have layered structures with different arrangements of [(NH4) [symbol: see text] [V2P2BO12]6] cluster anions within the layers. Crystal data: (NH4)2(C2H10N2)6[Sr(H2O)5]2[V2P2BO12]6 10H2O, monoclinic, space group C2/c (no. 15), a = 21.552(1) A, b = 27.694(2) A, c = 20.552(1) A, beta = 113.650(1) degrees, Z = 4; (NH4)2(C3H12N2)6[Sr(H2O)4]2[V2P2BO12]6 17H2O, monoclinic, space group I2/m (no. 12), a = 15.7618(9) A, b = 16.4821(9) A, c = 21.112(1) A, beta = 107.473(1) degrees, Z = 2; (NH4)3(C4H14N2)4.5[Sr(H2O)5]2[Sr(H2O)4] [V2P2BO12]6 10H2O, monoclinic, space group C2/c (no. 15), a = 39.364(2) A, b = 14.0924(7) A, c = 25.342(1) A, beta = 121.259(1) degrees, Z = 4. The differences in the three structures arise from the different steric requirements of the amines that lead to different amine-cluster hydrogen bonds.     

Kristallstruktur von Dipyridiniomethan-Monohalogenohydro-closo-Decaboraten(2–), [(C5H5N)2CH2][2-XB10H9]; X  Cl,Br, I

Crystal Structures of Dipyridiniomethane Monohalogenohydro-closo-Decaborates(2–), [(C₅H₅N)₂CH₂][2-XB₁₀H₉]; X = Cl, Br, I [B₁₀H₁₀]^2? reacts with chlorine, bromine and iodine or with N-halogenosuccinimide, yielding the monohalogenodecaborates [2-XB₁₀H₉]^2? (X = Cl, Br, I), which are separated by ion exchange chromatography on diethylaminoethyl(DEAE) cellulose from the starting compound and higher halogenated products. The X-ray structure determinations of the isotypic chloro and bromo compounds [(C₅H₅N)₂CH₂][2-XB₁₀H₉] (monoclinic, space group C2/c, Z = 8; for X ? Cl: a = 33.174(5), b = 7.2809(4), c = 16.2232(7) Å, β = 113.307(7)°; for X = Br: a = 33.525(11), b = 7.281(2), c = 16.297(4) Å, β = 113.62(2)°) and of the iodo compound [(C₅H₅N)₂CH₂][2-IB₁₀H₉] (monoclinic, space group P2₁, Z = 2, a = 7.143(3), b = 13.568(4), c = 9.479(7) Å, β = 97.57(5)°) show columns of substituted boron clusters [2-XB₁₀H₉]^2?, X = Cl, Br, I and bent dications [(C₅H₅N)₂CH₂]²⁺ along the shortest axis wich are assembled to alternating layers in the crystal lattice.     

Uranium (III) scorpionates: synthesis and structure of [(TpMe2)2U[N(C6H5)2]] and [(TpMe2)2U[N(SiMe3)2]

Reaction of [(Tp(Me)2)(2)UI] with KNR(2) (R = C(6)H(5), SiMe(3)) in tetrahydrofuran (THF) afforded the monomeric trivalent actinide amide complexes [(Tp(Me)2)(2)U[N(C(6)H(5))(2)]], 1, and [(Tp(Me)2)(2)U[N(SiMe(3))(2)]], 2. The complexes have been fully characterized by spectroscopic methods and their structures were confirmed by X-ray crystallographic studies. In the solid state 1 and 2 exhibit distorted pentagonal bipyramidal geometries. The U-NR(2) bond lengths in both complexes are the same but in complex 2 the greater steric demands of the N(SiMe(3))(2) ligand led to elongated U-N(pz) bonds, especially those opposite the amido ligand.     

Dialkylaluminum hydrazides derived from free hydrazine N2H4. Molecular Structures of [(MeC)2AlN2H3]2 and [(MeC)2Al]4(N2H2)2

The reaction of di(tert-butyl)aluminum hydride with hydrazine N2H4 afforded the hydrazide (Me3C)2AlN2H3, 1, by the release of elemental hydrogen. Compound 1 is a dimer in solution and in the solid state and possesses a six-membered Al2N4 heterocycle in a twist conformation with two intact N-N bonds. Further reaction of 1 with an excess of HAl(CMe3)2 yielded the tricyclic aluminum and nitrogen rich Al4N4 compound [(Me3C)2AlN2H2]2[Al(CMe3)2]2, 2, in which each N-N bond of a central six-membered Al2N4 ring similar to that of 1 is side-on-coordinated to an Al(CMe3)2 group. The structure of 2 may be interpreted as a dimer of the dialuminum hydrazide (Me3C)2Al-NH-NH-Al(CMe3)2.     

Cluster oxalate complexes [M3(mu3-Q)(mu2-Q2)3(C2O4)3]2- and [Mo3(mu3-Q)(mu2-Q)3(C2O4)3(H2O)3]2- (M = Mo, W; Q = S, Se): mechanochemical synthesis and crystal structure

Mechanochemical reaction of cluster coordination polymers 1infinity[M3Q7Br4] (M = Mo, W; Q = S, Se) with solid K2C2O4 leads to cluster core excision with the formation of anionic complexes [M3Q7(C2O4)3]2-. Extraction of the reaction mixture with water followed by crystallization gives crystalline K2[M3Q7(C2O4)3].0.5KBr.nH2O (M = Mo, Q = S, n = 3 (1); M = Mo, Q = Se, n = 4 (2); M = W, Q = S, n = 5 (3)). Cs2[Mo3S7(C2O4)3].0.5CsCl.3.5H2O (4) and (Et4N)1.5H0.5K{[Mo3S7(C2O4)3]Br}.2H2O (5) were also prepared. Close Q...Br contacts result in the formation of ionic triples {[M3Q7(C2O4)3](2)Br}5- in 1-4 and the 1:1 adduct {[Mo3S7(C2O4)3]Br}3- in 5. Treatment of 1 or 2 with PPh(3) leads to chalcogen abstraction with the formation of [Mo3(mu3-Q)(mu2-Q)3(C2O4)3(H2O)3]2-, isolated as (Ph4P)2[Mo3(mu3-S)(mu2-S)3(C2O4)3(H2O)3].11H2O (6) and (Ph4P2[Mo3(mu3-Se)(mu2-Se)3(C2O4)3(H2O)3].8.5H2O.0.5C2H5OH (7). All compounds were characterized by X-ray structure analysis. IR, Raman, electronic, and 77Se NMR spectra are also reported. Thermal decomposition of 1-3 was studied by thermogravimetry.     

Copper(I) complexes of fluorinated triazapentadienyl ligands: synthesis and characterization of [N[(C3F7)C(Dipp)N]2]CuL (where L = NCCH3, CNBut, CO; Dipp = 2,6-diisopropylphenyl)

Sterically demanding triazapentadiene [N[(C3F7)C(Dipp)N]2] H has been synthesized in good yield. It features a W-shaped ligand backbone in the solid state. [N[(C3F7)C(Dipp)N]2]H reacts with copper(I) oxide in acetonitrile leading to [N[(C3F7)C(Dipp)N]2]CuNCCH3. This copper adduct serves as an excellent precursor to obtain thermally stable [N[(C3F7)C(Dipp)N]2]CuCNBut and [N[(C3F7)C(Dipp)N]2]CuCO. IR spectroscopic data of these copper(I) isocyanide (CN = 2176 cm(-1)) and copper(I) carbonyl (CO = 2109 cm(-1)) complexes indicate that the [N[(C3F7)C(Dipp)N]2]- ligand is a fairly weak donor.     

Reaktionsprodukte von S7NH mit Nickel- und Kupfersalzen Darstellung und Struktur der Komplexe [(CH3)4N][Ni(S3N)(CN)2], [(C6H5)4As][Cu(S3N)2] und [(C6H5)4As][Cu(S3N)CI]

Metal Sulfur Nitrogen Compounds 18. Reaction Products of S₇NH with Nickel and Copper Salts. Preparation and Structures of the Complexes [Ch₃₄N][Ni(S₃N)(CN)₂], [(C₆H₅)₄As][Cu(S₃N)₂], and [(C₆H₅)₄AS][Cu(S₃N)Cl]. In the presence of MOH (M = K, [(CH₃)₄N]), S₇NH reacts with Ni(CN)₂ to yield, besides the three-nuclear complex M[(S₃NNi)₃S₂], the new mononuclear complex M[Ni(S₃N)(CN)₂]. The [(CH₃)₄N]⁺ salt is monoclinic, C2/m, a = 19.303(9), b =6.941(3), c=16.309(10) Å, β = 144.51⁰(2), Z = 4. The [Ni(S₃N)(CN)₂]- anion is planar, Ni being coordinated by one S₃N^? chelate ligand and by two CN^? ions. From the reaction of CuCI₂, S₇NH, and [Ph₄As]OH result the salts [Ph₄As][Cu(S₃N)₂] or [Ph₄As][Cu(S₃N)Cl], depending on the reaction conditions. [Ph₄As][Cu(S₃N)₂] is triclinic, P&1macr;, a = 7.073(3), b = 11.742(4), c = 16.439(6) Å α = 91.08°(3), β = 99.01°(3), γ = 91.58°(3), Z = 2. Two S₃N^? chelate ligands coordinate to Cu^I in a distorted tetrahedral arrangement. [Ph₄As][Cu(S₃N)Cl] is monoclinic, C2/c, a = 17.174(6), b = 13.650(5), c = 21.783(5) Å β = 100.45°(2), Z = 8. Cu^I is coordinated by one S₃N^? chelate ligand and one C1^?, resulting in a trigonal planar environment.     

[Et_4N]_2[Zn_2(OPh)_2Cl_4]的合成和晶体结构

ZnCl2, PhONa和Et4NCl稨2O在乙腈溶剂中反应合成了一种二核锌配合物[Et4N]2[Zn2(OPh)2Cl4]。X射线衍射结果表明,晶体属单斜晶系,C2/m空间群,晶胞参数 a = 14.1366(2), b=13.6985(5), c=9.3308(3)牛?107.851(2)o, V=1719.92(9)?,C28H50O2N2Zn2Cl4,Mr=721.24,Z=2,Dx=1.393g/cm3,μ(MoKα)=1.732mm—1,F(000)=756, R=0.0552, wR=0.1534, S=1.027。 配合物是由2个阳离子Et4N+和1个阴离子[Zn2(OPh)2Cl4]2—组成。阴离子[Zn2(OPh)2Cl4]2—包含着1个中心Zn2O2菱形平面。配合物中的2个锌原子通过2个苯酚中的氧原子桥连,每个锌原子还与2个氯原子配位形成变形四面体结构。     

Neue dimere Goldselenolate: Darstellung und strukturelle Charakterisierung von [(n-C4H9)4N]2[AuSSeCC(CN)2]2 und [(n-C4H9)4N]2[AuSe2CC(CN)2]2

New Dimeric Gold Selenolates: Preparation and Characterization of [(n-C₄H₉)₄N]₂[AuSSeC ? C(CN)₂]₂ and [(n-C₄H₉)₄N]₂[AuSe₂C ? C(CN)₂]₂ The preparation and structural characterization of the dimeric Au^I complexes of 1,1-dicyanoethene-2,2-thioseleonlate (i-mnts) and 1,1-dicyanoethene-2,2-diselenolate (i-mns), isolated as Bu₄N salts, are described. They are isotype (monoclinic, space group P2₁/c, Z = 2) with lattice parameters: (Bu₄N)₂[Au(i-mnts)]₂; a = 14.078(3) Å, b = 8.912(3) Å, c = 20.142(4) Å, β = 106.32(5)°; (Bu₄N)₂[Au(i-mns)]₂; a = 13.998(3) Å, b = 9.125(3) Å, c = 20.039(2) Å, β = 105.12(5)°. Ab initio Hartree-Fock calculations based on the experimentally determined structure yield a positive value of the Au? Au bonding order suggesting weak bonding interactions between the d¹⁰ metal centres.     

Trimerization of alkali dicyanamides M[N(CN)2] and formation of tricyanomelaminates M3[C6N9] (M = K, Rb) in the melt: crystal structure determination of three polymorphs of K[N(CN)2], two of Rb[N(CN)2], and one of K3[C6N9] and Rb3[C6N9] from X-ray powder diffractometry

The alkali dicyanamides M[N(CN)2] (M=K, Rb) were synthesized through ion exchange, and the corresponding tricyanomelaminates M3[C6N9] were obtained by heating the respective dicyanamides. The thermal behavior of the dicyanamides and their reaction to form the tricyanomelaminates were investigated by temperature-dependent X-ray powder diffractometry and thermoanalytical measurements. Potassium dicyanamide K[N(CN)2] was found to undergo four phase transitions: At 136 degrees C the low-temperature modification alpha-K[N(CN)2] transforms to beta-K[N(CN)2], and at 187degrees C the latter transforms to the high-temperature modification gamma-K[N(CN)2], which melts at 232 degrees C. Above 310 degrees C the dicyanamide ions [N(CN)2]- trimerize and the resulting tricyanomelaminate K3[C6N9] solidifies. Two modifications of rubidium dicyanamide have been identified: Even at -25 degrees C, the a form slowly transforms to beta-Rb[N(CN)2] within weeks. Rb[N(CN)2] has a melting point of 190 degrees C. Above 260 degrees C the dicyanamide ions [N(CN)2]- of the rubidium salt trimerize in the melt and the tricyanomelaminate Rb3[C6N9] solidifies. The crystal structures of all phases were determined by powder diffraction methods and were refined by the Rietveld method. alpha-K[N(CN)2] (Pbcm, a = 836.52(1), b = 46.90(1), c =7 21.27(1) pm, Z = 4), gamma-K[N(CN)2] (Pnma, a = 855.40(3), b = 387.80(1), 1252.73(4) pm, Z = 4), and Rb[N(CN)2] (C2/c, a = 1381.56(2), b = 1000.02(1), c = 1443.28(2) pm, 116.8963(6) degrees, Z = 16) represent new structure types. The crystal structure of beta-K[N(CN)2] (P2(1/n), a = -726.92(1), b 1596.34(2), c = 387.037(5) pm, 111.8782(6) degrees, Z = 4) is similar but not isotypic to the structure of alpha Na[N(CN)2]. alpha-Rb[N(CN)2] (Pbcm, a = 856.09(1), b = 661.711(7), c = 765.067(9) pm, Z = 4) is isotypic with alpha-K[N(CN)2]. The alkali dicyanamides contain the bent planar anion [N(CN)2]- of approximate symmetry C2, (average bond lengths: C-N(bridge) 133, C-N(term) 113 pm; average angles N-C-N 170 degrees, C-N-C 120 degrees). K3[C6N9] (P2(1/c), a = 373.82(1), b = 1192.48(5), c = 2500.4(1) pm, beta = 101.406(3) degrees, Z = 4) and Rb,[C6N9] (P2(1/c), a = 389.93(2), b = 1226.06(6), c = 2547.5(1) pm, 98.741(5) degrees, Z=4) are isotypic and they contain the planar cyclic anion [C6N9]3-. Although structurally related, Na3[C6N9] is not isotypic with the tricyanomelaminates M3[C6N9] (M = K, Rb).     

Dinitrogen functionalization with terminal alkynes, amines, and hydrazines promoted by [(eta5-C5Me4H)2Zr]2(mu2,eta2,eta2-N2): observation of side-on and end-on diazenido complexes in the reduction of N2 to hydrazine

Functionalization of the N2 ligand in the side-on bound dinitrogen complex, [(eta5-C5Me4H)2Zr]2(mu2,eta2,eta2-N2), has been accomplished by addition of terminal alkynes to furnish acetylide zirconocene diazenido complexes, [(eta5-C5Me4H)2Zr(C[triple bond]CR)]2(mu2,eta2,eta2-N2H2) (R = nBu, tBu, Ph). Characterization of [(eta5-C5Me4H)2Zr(C[triple bond]CCMe3)]2(mu2,eta2,eta2-N2H2) by X-ray diffraction revealed a side-on bound diazenido ligand in the solid state, while variable-temperature 1H and 15N NMR studies established rapid interconversion between eta1,eta1 and eta2,eta2 hapticity of the [N2H2]2- ligand in solution. Synthesis of alkyl, halide, and triflato zirconocene diazenido complexes, [(eta5-C5Me4H)2ZrX]2(mu2,eta1,eta1-N2H2) (X = Cl, I, OTf, CH2Ph, CH2SiMe3), afforded eta1,eta1 coordination of the [N2H2]2- fragment both in the solid state and in solution, demonstrating that sterically demanding, in some cases pi-donating, ligands can overcome the electronically preferred side-on bonding mode. Unlike [(eta5-C5Me4H)2ZrH]2(mu2,eta2,eta2-N2H2), the acetylide and alkyl zirconocene diazenido complexes are thermally robust, resisting alpha-migration and N2 cleavage up to temperatures of 115 degrees C. Dinitrogen functionalization with [(eta5-C5Me4H)2Zr]2(mu2,eta2,eta2-N2) was also accomplished by addition of proton donors. Weak Br?nsted acids such as water and ethanol yield hydrazine and (eta5-C5Me4H)2Zr(OH)2 and (eta5-C5Me4H)2Zr(OEt)2, respectively. Treatment of [(eta5-C5Me4H)2Zr]2(mu2,eta2,eta2-N2) with HNMe2 or H2NNMe2 furnished amido or hydrazido zirconocene diazenido complexes that ultimately produce hydrazine upon protonation with ethanol. These results contrast previous observations with [(eta5-C5Me5)2Zr(eta1-N2)]2(mu2,eta1,eta1-N2) where loss of free dinitrogen is observed upon treatment with weak acids. These studies highlight the importance of cyclopentadienyl substituents on transformations involving coordinated dinitrogen.     

The Synthesis and Crystallographic Characterization of Heterotrimetallic Linear Complex of [Et_4N][ (Ph_3P)_2{CuS_2WS_2Fe} Br_2]

1INTRoDUCTIONMolybdenum(Tungsten)-copper-sulfurandmolydenum(tungsten)-iron-sulfurcompoundshavebeenstudiedextensivelybecauseoftheirconnectionwithbiologicalprocesses[l,2j.Someheterotrimetalliccomplexeshavebeensynthesized,suchas[NEt'jtPh,p)sAgSzMoSzCu(CN))and[NEt'jtPh,P),AgS,MooCu(CN)jt3i,[l(CH,CH,)'j(PPh,)2{AgS2WS2Cu}(CN)jt4i,[(CH,CH2)4j(PPh,)2{AgS,WOCu}(CN)j('3,butheterotrimetal1iccomplexescontainingtungsten,copper,andironatomshaveseldombeenreported.Onecomplexofthiskindha…     

Studies on solid state reactions of coordination compounds. LXIII. Solid state synthesis of a series of tetranuclear Mo(W)—Ag mixed-metal clusters. Crystal structures of [(n-Bu)4N]3[MoOS3Ag3Br4] and [(n-Bu)4N]3[WS4Ag3Cl4]

A series of tetranuclear Mo(W)-Ag mixed-metal clusters have been synthesized by making use of the solid state reactions of [NH₄]₂[MYS₃](M= Mo, W; Y= O, S), AgX(X= Cl, Br, I) and (n-Bu)₄NX' (X' =Cl, Br), two of which [(n-Bu)₄N]₃[MoOS₃Ag₃Br₄] (1) and [(n-Bu)₄N]₃[WS₄Ag₃Cl₄] ( 2 ) have been structurally characterized by X-ray analysis. The crystal data: 1 , cubic, P4 3m, αequals;12.093(4) Å, Z=1, R =0.076; 2 , cubic, P4 3m, αequals;12.059(2) Å, Z =1, R =0.075. The cluster anion core [Ag₃MS₃X'] of the two compounds can be viewed as a cube in which the four metal atoms and the four non-metal atoms are statistically distributed, respectively. Substitution reaction with PPh₃ ligand is also discussed for this type of tetranuclear clusters.     

New tetraphosphane ligands {(X2P)2NC6H4N(PX2)2} (X = Cl, F,OMe, OC6H4OMe-o): synthesis, derivatization, group 10 and 11 metal complexes and catalytic investigations. DFT calculations on intermolecular P...P interactions in halo-phosphines

The reaction of p-phenylenediamine with excess PCl 3 in the presence of pyridine affords p-C 6H 4[N(PCl 2) 2] 2 ( 1) in good yield. Fluorination of 1 with SbF 3 produces p-C 6H 4[N(PF 2) 2] 2 ( 2). The aminotetra(phosphonites) p-C 6H 4[N{P(OC 6H 4OMe- o) 2} 2] 2 ( 3) and p-C 6H 4[N{P(OMe) 2} 2] 2 ( 4) have been prepared by reacting 1 with appropriate amount of 2-(methoxy)phenol or methanol, respectively, in the presence of triethylamine. The reactions of 3 and 4 with H 2O 2, elemental sulfur, or selenium afforded the tetrachalcogenides, p-C 6H 4[N{P(O)(OC 6H 4OMe- o) 2} 2] 2 ( 5), p-C 6H 4[N{P(S)(OMe) 2} 2] 2 ( 6), and p-C 6H 4[N{P(Se)(OMe) 2} 2] 2 ( 7) in good yield. Reactions of 3 with [M(COD)Cl 2] (M = Pd or Pt) (COD = cycloocta-1,5-diene) resulted in the formation of the chelate complexes, [M 2Cl 4- p-C 6H 4{N{P(OC 6H 4OMe- o) 2} 2} 2] ( 8, M = Pd and 9, M = Pt). The reactions of 3 with 4 equiv of CuX (X = Br and I) produce the tetranuclear complexes, [Cu 4(mu 2-X) 4(NCCH 3) 4- p-C 6H 4{N(P(OC 6H 4OMe- o) 2) 2} 2] ( 10, X = Br; 11, X = I). The molecular structures of 1- 3, 6, 7, and 9- 11 are confirmed by single-crystal X-ray diffraction studies. The weak intermolecular P...P interactions observed in 1 leads to the formation of a 2D sheetlike structure, which is also examined by DFT calculations. The catalytic activity of the Pd(II) 8 has been investigated in Suzuki-Miyaura cross-coupling reactions.     

Synthesis and structures of selected benzamidinates of Li, Na, Al, Zr and Sn(II) using the C1-symmetric ligands [N(SiMe3)C(C6H4Me-4 or Ph)NPh]-

Several compounds based on the C(1)-symmetric ligands [N(R)C(Ar)NPh]- [abbreviated as B1 (Ar = C(6)H(4)Me-4) or B2 (Ar = Ph), R = SiMe(3)] are reported. They are the crystalline metal benzamidinates [Li(mu:kappa2-B1)(OEt2)](2) (1), [Al(kappa2-B1)2Me] (2), [Al(kappa2-B1)2X] [X = Cl/Me, 1 : 1 (3)], [Sn(kappa2-B1)2] (4), Zr(kappa2-B1)2Cl2 (5), [Zr(kappa2-B1)3Cl] (6), [Na(mu:kappa2-B1)(tmeda)]2 (7), K[B1] (8), Li(B2)(OEt2) (9) and Zr(kappa2-B1)3Cl (10) and the known benzamidine Z-H2NC(C6H4Me-4) = NPh (11). They were prepared by (i) insertion of the nitrile 4-MeC6H4CN (1, 7, 8, 11) or PhCN (9) into the appropriate M-N(R')Ph [R' = R and M = Li (1, 9), Na (7), K (8)] bond and subsequent hydrolysis for 11 [R' = H and M = Li], or (ii) a ligand transfer reaction using the lithium amidinate 1 and Al(Me)2Cl (2, 3), SnCl2 (4) or ZrCl4 (5, 6), or Li(B2) and ZrCl4 (10). The X-ray structures of 1, 2, 3, 4, 6b (i.e..3PhMe) 7, and 11 are presented. Exploratory polymerisation experiments are described, using 2, 5 or 6 as a procatalyst with methylaluminoxane (MAO) (Al : Zr ca. 500 : 1) as promoter. Thus toluene solutions were exposed to C2H4 under ambient conditions; while 2 was unresponsive, 5 and 6 showed modest activity in the formation of polyethylene.