Iron complexes of N-allylbenzotriazoles

Sodium benzotriazolide reacts with π-C₃H₅Fe(CO)₃I to give 1-N-allylbenzotriazoletricarbonyliron (I). The same product and the isomeric complex, 2-N-allylbenzotriazoletricarbonyliron (II), have been prepared independently, from the corresponding N-allylbenzotriazoles and Fe₂(CO)₉. The IR, ¹H NMR, and mass spectra of the complexes are reported. The structure of isomer I has been determined by X-ray diffraction. The crystals are monoclinic, P2₁/c, a = 10.65(1), b = 9.95(1), c = 12.90(1) Å, β = 113.69(7)°, d_calc = 1.39 g cm^?3, Z = 4.     

Crystalline and molecular structures of two halogenated propionamides CF2XCF2CONH2 (X = H, Cl)

Using the XRD method, the crystalline and molecular structures of two halogenated propionamides, CF₂XCF₂CONH₂, X = H (I) and Cl (II), have been studied. Crystals I and II are monoclinic: space group P2₁/c, Z = 4; (I) a = 10.967 Å, b = 5.406 Å, c = 10.063 Å, β = 107.86°; (II) a = 11.979 Å, b = 5.608 Å, c = 10.042 Å, β = 99.31°. Structures I and II were solved by the direct method and refined by the full-matrix least-square method to R = 0.112 (I) and 0.139 (II) over all 1299 (I) and 1175 (II) independent measured reflections (a CAD-4 autodiffractometer, λMoK _α).     

X-ray and mössbauer studies of tricyclohexyltin(IV) halides. The crystal structures of (cyclo-C6H11)3SnX (X = F,Br and I)

The structures of tricyclohexyltin fluoride (I), bromide (II) and iodide (III) have been determined by X-ray analysis. Compound I crystallizes in the space group P2₁/m with a = 10.422(6), b = 17.238(9), c = 5.769(3) Å, β = 104.6(1)° and Z = 2. Compounds II and III crystallize in the space group Pcmn with a = 10.427(6), b = 16.914(9), c = 11.366(6) Å, Z = 4; and a = 10.400(6), b = 16.900(10), c = 11.400(4) Å, Z = 4, respectively. All three structures consist of discrete tetrahedral (cyclo-C₆H₁₁)₃SnX units.The temperature dependence of the Mössbauer resonance areas has been examined in order to obtain information about the relationship between chemical structure and lattice dynamics.     

Complexes of N-methyl-4-mercaptopiperidine with some metal ions

Complexes of N-methyl-4-mercaptopiperidine in its zwitterionic form with Co(II) and Zn(II) salts, and in anionic form with Cu(I) and Ag(I) salts have been prepared. Stoichiometry of the complexes, Co(HRS)₂COX₄ (X = Cl and Br), Co(HRS)₂X₂ (X = ClO₄, NO₃), Co(HRS)₃X₃ (X = NO₃, ClO₄), Zn(HRS)₂ZnX₄ (X = Cl and Br), Zn(HRS)₂(NO₃)₂, Ag(RS) and Cu(RS), have been established by chemical analysis. The solid complexes have been further characterized by IR and electronic spectra measurements.     

Syntheses and Crystal Structures of Quinidinum-Zinc(II)-Trichloride and Quinidinum Iron(III) Tetrachloride Hydrogen Chloride Hydrate

A mononuclear coordination complex, quinidinum-zinc(II)-trichloride (I), and a multi-component ionic complex, quinidinum iron(III) tetrachloride hydrogen chloride hydrate (II), have been synthesized and characterized by elemental analyses, IR spectra, and single crystal X-ray diffraction (CIF files nos. 1497628 (I) and 1497629 (II)). The weak hydrogen-bonding interactions exist in both complexes I and II. Both complexes crystallize in the chiral space groups with the absolute configuration. Complex I crystallizes in the orthorhombic space group P2₁2₁2₁ with a = 7.6651(6), b = 11.4923(9), c = 24.653(2) Å, and Z = 4. Complex II crystallizes in the monoclinic space group P2₁ with a = 6.6425(15), b = 18.660(4), c = 10.958(3) Å, β = 104.973(3), and Z = 2.     

Crystal structures of two macrocyclic diterpenoid photoproducts

The crystal structures of two macrocyclic diterpenoid photoproducts, the chemistry of which has been described in the preceding paper have been determined at 295 K.Compounds I (C₂₀H₂₆O₃) and II (C₂₂H₃₀O₅) are both orthorhombic, P2₁2₁2₁. In I. a = 24.18(1), b = 11.841 c=5.984(2) Å. Z=4. the structure being refined by least squares to a residual of 0.063 for 1234 “observed” reflections. For II. a = 24.30(1), b = 9.413(5). c = 9.149(5) Å. Z = 4 (R = 0.070, 982 “observed” reflections).     

The crystal structures of 1-allyl-1-bromo-3,4-benzo-1-telluracyclopentane [C8H8Te(C3H5)Br], 1-phenacyl-1-bromo-3,4-benzo-1-telluracyclopentane [C8H8Te(C8H7O)Br] and 1-deuteromethyl-1-iodo-3,4-benzo-1-telluracyclopentane [C8H8Te(CD3)I]; the trans effect in organotellurium bromides and iodides

The crystal structures of the title compounds have been determined from three-dimensional X-ray counter data.C₈H₈Te(CH₂CHCH₂)Br (I) is orthorhombic, space group Pbca with a 9.642(1), b 25.586(7), c 9.680(3) Å, Z = 8. The structure has been refined to R 5.2% for 1262 observed reflections.C₈H₈Te(CH₂COPh)Br (II) is orthorhombic, space group Pccn with a 23.593(6), b 14.337(3), c 9.180(2) Å, Z = 8. R = 5.5% for 1374 reflections.C₈H₈Te(CD₃)I (III) is orthorhombic, space group Pbca with a 11.200(3), b 15.976(2), c 23.328(3) Å, Z = 16. R = 5.6% for 2142 reflections.In I and II, tellurium is coordinated in an approximately octahedral geometry by the organic residues and three halogen contacts, with TeC and TeBr distances in the ranges 2.14(1)–2.19(1) Å and 3.328(2)–3.368(2) Å in (I) and 2.12(1)–2.18(1) Å and 3.292(2)–3.391(2) Å in II.In III, each of the two crystallographically independent complexes has tellurium coordinated in a distorted octahedral geometry. The TeC bond lengths are 2.10(2)–2.16(2) Å. In each case two TeI distances are in the range 3.596(2)–3.688(2) Å and a third, longer interaction (3.870(2) and 4.112(2) Å) completes the coordination.In each of the structures I–III the three covalent TeC bonds are oriented cis within the octahedra and exert a trans bond-lengthening effect on the Tehalogen interactions, precluding covalent-type bonding; the structures are essentially ionic, (C₈H₈TeR)⁺ cations and halide anions forming extended arrays.     

Über polystannane: II. I(t-Bu2Sn)4I,ein 1,4-difunktionelles tetrastannan

The compound I(t-Bu₂Sn)₄I has been synthesized by controlled cleavage of the related cyclotetrastannane (t-Bu₂Sn)₄ with iodine in toluene. Both compounds have been investigated by mass, NMR and vibrational spectra. I(t-Bu₂Sn)₄I: δ(¹¹⁹Sn_terminal) 67.7, δ(Sn_central) 17.4 ppm; ¹J(SnSn) 2199 (terminal-central) and 1575 (central-central), ²J(SnSn) 20 (terminal-central), ³J (SnSn) 307 Hz (terminal-terminal); ν(SnSn) 119, ν(SnI) 167 cm^?1. (t-Bu₂Sn)₄: δ(Sn) 87.4 ppm; ν(SnSn) 125 cm^?1. The crystal structure of I(t-Bu₂Sn)₄I has been determined (R = 0.071): bond lengths SnSn 289.5(1) (terminal-central) and 292.4(1) (central-central), SnI 275.3(1) pm. The conformation of the chain ISn₄I is all trans.     

The isolation of intermediates in hydrogen halide additions to some iridium complexes

The complexes [Ir(cod)L_n]PF₆(I, L = PPh₃, PMePh₂; n = 2. L = PMe₂Ph; n = 3) react with HX to give [IrHX(cod)L₂]PF₆ (II, L = PMePh₂ or PMe₂Ph) or [IrHX₂(cod)(PPh₃)] (III). The intermediates [IrX(cod)L₂] have, in two cases (L = PMePh₂, X = I, Br), been directly isolated from the reaction mixtures at 0°C, and are also formed from I with KX (L = PPh₃, X = Cl; L = PMePh₂, X = Cl, Br, I); these intermediates protonate to give II (L = PMePh₂), or an equimolar mixture of III and I (L = PPh₃, X = Cl). Surprisingly, I₂ reacts with I in MeOH to give III (L = PPh₃). The stereochemistries of II and III were determined by < ¹H NMR and especially by new methods using ¹³C NMR spectroscopy. The complexes I exhibit a Lewis acid reactivity pattern.     

Haloalkyl complexes of the transition metals: IV. The formation of a cationic ylide complex of platinum(II) from a chloromethylplatinum(II) complex and the crystal structures of cis-[Pt(CH2PPh3)X(PPh3)2]I (X = Cl or I)

The reactions of Pt(PPH₃)₄ and Pt(C₂H₄)(PPh₃)₂ with CH₂ClI have been investigated. The product of the reaction of Pt(PPh₃)₄ with CH₂ClI is the cationic ylide complex cis-[Pt(CH₂PPh₃)Cl(PPh₃)2][I], whereas the reaction of Pt(C₂H₄)-(PPh₃)₂ gives the oxidative addition product Pt(CH₂Cl)I(PPh₃)₂. Reaction of cis- or trans-Pt(CH₂Cl)I(PPh₃)₂] with PPh₃ gives the complex cis-[Pt(CH₂PPh₃)-Cl(PPh₃)₂][I]. The structures of the complexes cis-[Pt(CH₂PPh₃X(PPh₃)₂][I] (where X = Cl or I) have been determined by X-ray crystallography. Both complexes crystalize in the monoclinic space group P2₁/n. For X = Cl a 1388.6(7), b 2026.7(10), c 1823.9(9) pm, β 96.51(2)° and R converged to 0.075 for 3542 observed reflections; structural parameters Pt-Cl 240(1), Pt-C(3) 212(2), Pt-P(2) (trans to Cl) 235(1) and Pt-P(1) (trans to CH₂PPh₃) 233(1) pm; Cl-Pt-C(3) 86.9(5), C(3)-Pt-P(2) 91.8(5), P(2)-Pt-P(1) 97.0(2) and P(1)-Pt-Cl 85.1(2)°. For X = I, a 1379.4(7), b 2044.4(10), c 1840.0(9) pm, β 96.09(2)° and R converged to 0.071 for 4333 observed reflections; structural parameters Pt-I 266(1), Pt-C(3) 212(2), Pt-P(2) (trans to I) 226(1) and Pt-P(1) (trans to CH₂PPh₃ 233(1) pm; I-Pt-C(3) 87.2(5), C(3)-Pt-P(2) 91.5(5), P(2)-Pt-P(1) 96.5(2) and P(1)-Pt-I 85.6(1)°. Some other complexes of the type cis-[Pt(CH₂PPh₃)X(PPh₃)₂]Y are also described.     

The crystal structures of the 1-methyl-3,4-benzo-1-telluracyclopentane and 1-phenyl-1-telluracyclopentane cations in their tetraphenylborate salts,C8H8TeMe+ BPh4− and C4H8TePh+ BPh4−

The crystal structures of C₈H₈TeMe⁺ BPh₄^? (I) and C₄H₈TePh⁺ BPh₄^? (II) have been determined from three-dimensional X-ray counter data.I is monoclinic, space group P2₁/n with a 9.175(1), b 17.402(3), c 16.998(3) Å, β 98.92(6)°, Z = 4, R = 5.1% for 1641 observed reflections.II is triclinic, space group P$\text{1}$ with a 9.635(3), b 17.721(3), c 16.858(8) Å, α 89.77(2), β 104.36(4), γ 90.16(2)°, Z = 4, R = 9.0% for 6466 observed reflections.In both I and II tellurium is three-coordinate in a pyramidal geometry, with TeC distances in the range 2.07(1)–2.14(1) Å (I) and 2.10(1)–2.17(1) Å (II). In both structures short contacts of 3.4—3.5 Å occur between tellurium and carbon atoms of the tetraphenylborate anion.     

Palladium(II) halide complexes with 2,5-dimethyl-, 2-amino-, 2-amino-5-methyl-, 2-ethylamino- and 2-mercapto-5-methyl-1,3,4-thiadiazole

Some palladium(II) halide complexes with 2,5-dimethyl- (DTZ), 2-amino- (ATZ), 2-amino-5-methyl- (MATZ), 2-ethylamino- (EATZ) and 2-mercapto-5-methyl-1,3,4-thiadiazole (MTTZ) have been prepared and studied: PdX₂ · 2L (L = DTZ, ATZ, MATZ : X = Cl, Br, I; L = EATZ: X = Br, I; L = MTTZ: X = I), PdCl₂ · 2.5EATZ, PdCl₂ · 3MTTZ, PdBr₂ · 1.5MTTZ and PdX₂ · L (L = DTZ, ATZ, MATZ, EATZ: X = Cl, Br; L = MTTZ: X = Cl(H₂O), Br). In the PdX₂ · 2L, PdCl₂ · 2.5EATZ and PdCl₂ · 3MTTZ complexes the palladium ions are cis-(2X, 2L)-coordinated, the coordination sites being N_ring for DTZ, NR₂ for ATZ, MATZ, EATZ and C = S for MTTZ. PdBr₂ · 1.5MTTZ may be formulated as cis[PdBr₂-2L] · [PdBr₂ · L]. In the PdX₂ · L complexes the ligand very likely acts as bidentate by using a ring-nitrogen atom as the second coordination site.     

Organostibines as ligands. Synthesis of dimethyl(α-picolyl)stibine,dimethyl(8-quinolyl)stibine,and (R;S)-methylphenyl(8-quinolyl)stibine and some transition metal derivatives

The unsymmetrical mono-tertiary stibines dimethyl(α-picolyl)stibine (picstib), dimethyl(8-quinolyl)stibine (quinstib), and (R;S)-methylphenyl(8-quinolyl)stibine (R;S-quinstib) have been synthesised and the square-planar complexes [MX₂(picstib)], [MX₂(quinstib)] (where M = Pd or Pt and X = Cl, Br, I or SCN) and [MCl₂(R;S-quinstib)] (where M = Pd or Pt) isolated. The thiocyanato derivatives display linkage isomerism. The octahedral complexes [M(CO)_4-(picstib)] and [M(CO)₄(quinstib)] have also been prepared from the metal hexacarbonyls and the appropriate ligands by UV irradiation in tetrahydrofuran.     

Kristall-und molekülstrukturen zweier modifikationen de hexaphenyldigermylsulfids (C6H5)3GeSGe(C6H5)3

en Two differnt crystal modifications of hexaphenyldigermanium sulfide (C₆H₅GeSGe(C₆H₅)₃ (I and II were obtained by crystallization from hot benzene/methanol or form ethanol at 20°C. Single crystal X-ray structural analyses for both I (low temperature data at ?130°C) and II (at 20°C) (I, R = 0.046; II, R = 0.048) were performed. I is monoclinic, P2¹/c, with a = 11.020(3), b = 15.473(3), c 18.606(3) »,π = 106.92(2)°, Z = 4; II is orthorhombic, P2₁2₁2₁, with a = 2.617(2), b = 17.345(3), c = 18.408(3) », Z = 4.The molecules have different conformeric structures with respect to a rotation of the (C₆H₆)₃Ge groups around the Ge bonds with very similar bond lenghts and angles. Bond data for I(II) are: GeS 2.212(1) and 2.261(1) » (2.227(2) and 2.240(2) »); GeC 1.933(4) ? 1.971(4), mean 1.945(5) » (1.931(7)?1.954(7), mean 1.943(4) »); GeSGe 111.2(1)° (110.7(1)°). The Ge bond lenghts are comparable to those in thiogermanates and do not indicate significant π-bond contributions.     

Barreleneiridium(I) complexes. Crystal structures of [Ir(Me3TFB)(η6-C6H4Me2)]ClO4 and [Ir(TFB)(η5-PhNPh2)]BF4·CH2Cl2 (TFB = tetrafluorobenzobarrelene)

A new series of cationic areneiridium(I) complexes of formula [Ir(barrelene)(arene)]⁺ or [Ir(barrelene)(PhNRPh)]⁺ (R= Ph or H) have been synthesized from neutral iridium complexes of the type [IrY(barrelene)]_x (barrelene = Me₃TFB, Y = Cl or OMe (x = 2), Y = acac (x = 1); barrelene = TFB, Y = OMe (x = 2), Y = acac (x = 1)). The crystal structures of [Ir(Me₃TFB)(1,4-C₆H₄Me₂)]ClO₄ and [Ir(TFB)(PhNPh₂)]BF₄·CH₂Cl₂ have been determined by X-ray diffraction. They crystallize in the space groups Pbca and Pna2₁ respectively with lattice constants of 17.6947(11), 15.8072(10), 16.0019(11) Å and 9.8059(2), 20.8097(9), 14.3367(4) Å. Final R factors were 0.063 and 0.042 for the observed data. Both complexes show a staggered arrangement between the arene and the TFB moieties and deviation from planarity of the coordinated arene ligands. In the second complex the IrC and NC distances, the CNC angle, the type of arene puckering, and the spectroscopic data indicate a distortion of the coordinated arene towards a η⁵-coordinated iminocyclohexadienyl form.     

Distorted tetrahedral copper(I)′complexes of 2,2′bi-4,5-dihydrothiazine and 2,2′-bi-2-thiazoline

The copper(I) complexes [Cu(btz)₂](BPh]₄(I) and [Cu₂(bt)₄][ClO₄]₂ (II) have been prepared (btz = 2,2′-bi-4,5-dihydrothiazine and bt = 2,2′-bi-2-thiazoline). Crystals of (I) are orthorhombic with a = 10.927(8), b = 11.743(8), c = 15.000(6) A, Z = 2, spacegroup P2₁2₁2. Crystals of (II) are monoclinic with a = 21.928(11), b = 11.925(8), c = 14.716(11) A, β = 103.6(1), Z = 8, spacegroup C2/c. 2121 and 2204 independent reflections have been measured on a diffractometer and the structures refined R 0.061 to R 0.063 respectively. In the cation of (I) the two btz ligands are coordinated via the α-di-imine groups (Cu-N 2.010(6), 2.024(6)Å). The resulting CuN₄ coordination geometry is a flattened tetrahedron with a dihedral angle of 68.9° between the two “CuN₂” planes. It is suggested that this distortion is an intrinsic property of the molecule associated with metal-to-ligand d_π-p_π* charge transfer rather than a consequence of lattice packing effects. In the dimeric cation (II), each copper(I) ion is bonded to the α-di-imine group of one bt molecule (A) but with appreciably different CuN bond lengths (2.277(6), 1.999(5)Å), to one nitrogen atom of a second ligand molecule (B) in the trans configuration (CuN 1.961(5)Å) and to one sulphur atom (CuS 2.428(2)Å) of a third ligand molecule (C). The coordination geometry is a very distorted tetrahedron if a very weak interaction (Cu…S 3.039(2)Å) with a sulphur atom of ligand B is discounted. It is suggested that the different structure arise from the different “bites” of the two ligands.     

The preparation and X-ray crystal and molecular structure of (α,1,2-η-6-methylbenzyl) bis(triphenylphosphine)rhodium(I)

Reaction of [RhCl(PPh₃)₃] with [o-MeC₆H₄CH₂MgBr] affords high yields of the non-fluxional complex, [Rh(CH₂C₆H₄Me)(PPh₃)₂] which has been shown crystallographically to contain a 1-3-η-benzyl group bound through the phenyl carbon atom that is not substituted with the methyl group. Crystals of this compound are triclinic, space group P$\text{1}$, with a = 10.561(6). b = 17.705(3), c = 10.934(4) Å, α = 80.69(3), β = 116.86(4), γ = 102.30(4)° and Z = 2. The structure was solved via the heavy-atom method and refined to R = 0.032 using 5379 diffractometer data with I > 1.56(I). Attempts to prepare π-bonded xylylene complexes from this compound by reaction with base have been unsuccessful, but protonation followed by recrystallisation from acetone gives [Rh{(CH₃)₂CO}₂(PPh₃)₂]BF₄.     

Rhodium(III) and iridium(III) olefin complexes containing the tridentate ligand 1,6-bis(diphenylphosphino)-trans-hex-3-ene: crystal and molecular structure of trichloro-1,6-bis(diphenylphosphino)-trans-hex-3-eneiridium(III).

The olefin complexes RhCl₃(BDPH), RhClBr₂(BDPH), IrCl₃(BDPH), IrClBr₂(BDPH), IrCl(CH₃)I(BDPH), IrHCl₂(BDPH) and IrHBr₂(BDPH); BDPH = 1,6-bis(diphenylphosphino)-trans-hex-3-ene, have been prepared by oxidative-addition reactions of RhCl(BDPH) and IrCl(BDPH) and characterised by I.R. and ¹H NMR spectra. A single crystal X-ray determination of the structure of IrCl₃(BDPH) shows the crystals to be orthorhombic, a = 16.1636(13), b = 20.2927(7), c = 17.1916(6)Å, Z = 8, space group Pbca, ?_obs = 1.76, ?_calc = 1.77 g cm^?3. The structure was solved by conventional methods and refined by use of full-matrix least-squares equations to final residuals R = 0.041 and R_w = 0.052 for 2926 observed reflections.The complex is monomeric with an octahedral coordination geometry consisting of the tridentate olefin(phosphine)₂ BDPH ligand (arranged such that the phosphorus atoms are mutually trans, and the three chloride ligands. Distances observed are Ir-P 2.382, 2.389(2)Å, Ir-Cl 2.358, 2.387 (trans to olefin), 2.371(2)Å, Ir-C(olefin) 2.274, 2.277(10)Åf, C=C 1.352(14)Å. The olefin is inclined at an angle of 28° to the Ir, P(1), P(2), Cl(2) plane. The structure is compared and contrasted with the known structures of IrCl(BDPH) and IrH₂Cl(BDPH).     

The chemistry and the sterechemistry of Poly(N-Alkyliminoalanes: XIII. The crystal and molecular structure of the hexamers (ClAlN-i-Pr)6 and (Me0.83H0.17AlN-i-Pr)6MeAlN-i-Pr)6

The crystall and molecular structures of (ClAlN-i-Pr)₆ (I), and of (Me_0.83H_0.17AlN-i-Pr)₆(MeAlN-i-Pr)₆ have been determined by single crystal three-dimensional X-ray analysis. Block-matrix least-squares refinements led to conventional R factor of 0.039 for I and 0.037 for II. The compounds are isostructural, as the cage molecules consist of a prismatic hexagonal framework, (AlN)₆, similar to that observed for the parent hydrogenated analogue (HAlN-i-Pr)₆.Some differences in bond distances and angles are discussed, in connection with the different Al-bonded substituents. Crystal data: I, trigonal space group R$\text{3}$; a = 17.083(2), c = 9.652(1); Z = 3; D_c 1.46 g cm^?3; II, trigonal space group R$\text{3}$, a = 17.378(3), c = 9.706(3) »; Z = 3; D_c 1.15 g cm^?3.     

Chirality changes in reactions of asymmetric molybdenum complexes

Optical rotatory dispersion and circular dichroism studies have allowed the determination of the changes in configuration at the molybdenum center upon displacement of carbonyl and iodide in neomenthylcyclopentadienyl—Mo(allyl)(NO)X systems. Displacement of carbonyl by iodide occurs with retention of configuration. Replacement of iodide with benzenesulfonate followed by replacement of the sulfonate with iodide occurs stereospecifically with net retention of configuration. In the case of cyclopentadienylMo(cyclooctenyl)(NO)I, the enantiomers were separated via a spontaneous resolution through crystallization of the complex in the space group P2₁2₁2₁. These studies have allowed the correlation not only of the absolute configuration at the metal center with CD studies, but also have established that a long wavelength optically active transition at approximately 400 nm can be correlated with endo-exo isomerism. Comparison of the rates of interconversion suggest that endo to exo isomerization occurs via a clockwise rotation of the allyl in the (R)-isomer. Crystallographic details: (—)-(S)-(NMCp)Mo(allyl)(NO)I crystallizes in the space group P2₁2₁2₁ with a 7.221(1), b 12.686(7), c 21.603(7) Å, Z = 4, V = 1979(2) ų; R₁ = 0.039, R₂ = 0.046; (—)-(S)-(Cp)Mo(cyclooctenyl)(NO)I crystallizes in the space group P2₁2₁2₁ with a 8.466(1), b 10.449(2), c 16.372(2) Å, Z = 4, V = 1448.3(6), R₁ = 0.038, and R₂ = 0.046.