Organometallic polymorphism. Synthesis and structural characterization of two forms of [Ru(η6-C6H6)(η6-C6H4(CH3)COOCH3)][BF4]2 and the phase transition in [Ru(η5-C5H5)(η6-C6H5OH)][PF6]

The synthesis and structural characterization of the complex [Ru(η⁶-C₆H₆)(η⁶-C₆H₄(CH₃)COOCH₃)] [BF₄]₂ (2) and of its precursor [Ru(η⁶-C₆H₄(CH₃)COOCH₃)Cl₂]₂ (1) are reported. Compound (2) has been characterized in two polymorphic modifications (2a and 2b) and the molecular organization in the solid state has been investigated. The complex [Ru(η⁵-C₅H₅)(η⁶-C₆H₅OH)][PF₆] (3) has also been investigated; it has been shown to possess a disorder similar to that observed in the high temperature phase of related systems such as [Ru(η⁵-C₅H₅)(η⁶-C₆H₆)][PF₆].     

The X-ray crystal structure of di-η5-cyclopentadienylthiophenolatoamminemolybdenum(IV) hexafluorophosphate solvate [Mo(η5-C5H5)2(NH3)(SC6H5)][PF6] · (CH32CO

Crystals of [Mo(η⁵-C₅H₅)₂(NH₃)(SC₆H₅)][PF₆] · (CH₃)₂CO solvate are monoclinic, space group P2₁/n, a 9.777(1), b 11.6343(2), c 19.656(4) Å, β 93.60(1)°, V 2231-46 ų, Z  D_c 1.617 g cm⁻³, μ(Mo-K_α) 7.21 cm⁻¹. The structure was solved by Patterson and difference Fourier electron density synthesis and refined to R (F)  0.047 and R_w(F)  0.057 for 3293 observed reflections. The molybdenum atom has the usual distorted tetrahedral geometry comprising the two MoCp (Cp  η⁵-C₅H₅) ring normals (MoCp 1.988(13), 1.989(15) Å), one Mo-NH₃ (MoN 2.226(12) Å), and one MoSc₆H₅ (MoS 2.465(5) Å). Extended HMO and steric energy calculations were made in order to account for the geometry adopted by the thiolato ligand in this complex.     

Comparative studies of the photochemical and thermal reactivities of the molybdenum-molybdenum single bond in [Mo2(η5-C5H5)2(CO)6] and triple bond in [Mo2(η5-C5H5)2(CO)4] towards nitrite and nitrate

Irradiation at λ = 507 and 391 nm of [Mo₂(η⁵-C₅H₅)₂(CO)₆] in a degassed tetrahydrofuran (THF) or THF-MeOH solution containing nitrite gives [Mo(η⁵-C₅H₅)₂NO] and several oxo complexes including [{Mo(η⁵-C₅H₅)(O)₂}₂O] in good yields. The quantum yields for the disappearance of [Mo₂(η⁵-C₅H₅)₂(CO)₆] in the reaction with NO₂⁻ depend on the nitrite concentration, thus suggesting participation of the metal-radical intermediate in the reduction of nitrite. Reactions of [Mo₂(η⁵-C₅H₅)₂(CO)₄] with nitrite or nitrate in the dark give the same nitrosyl and oxo complexes as above. An oxygen atom in nitrite or nitrate is mainly transferred onto the molybdenum atom both in the photochemical and the dark reactions.     

Synthesis and Crystal Structure of [CpRu(η5-C5H5)(dppc)Cl][PF6]

The title complex [Ru(η5-C5H5)(dppc)Cl][PF6] has been synthesized by the reaction of [Ru(η5-C5H5)(PPh3)2Cl] with [dppc][PF6] (1,1'-bis(diphenylphosphino)cobaltocenium hexaflurophospate) in CH2Cl2, and its crystal structure was determined by single-crystal X-ray diffraction analysis. It crystallizes in monoclinic, space group P21/n with a = 15.754(8), b =13.704(7), c=19.120(10) (A),β=106.148(9)°, V=3965(4) (A)3, Z=4, C40H35Cl3CoF6P3Ru, Mr=988.94, Dc=1.657 g/cm3, F(000) = 1984 and μ(MoKα) = 1.181 mm-1. The final R = 0.0425 and wR = 0.1001 for 7002 independent reflections. The title complex shows a mononuclear Ru(Ⅱ)capped by an η5-Cp ring, a chelating η2-dppc and a terminal chloride to assume a three-legged piano-stool configuration.     

High first hyperpolarizability and perfectly aligned crystal packing for an organometallic compound [Fe(η5-C5H5)((R)–PROPHOS)(p-NCC6H4NO2)][PF6]·CH2Cl2

The molecular first hyperpolarizability, β, and the X-ray crystal structure of the complex [Fe(η⁵-C₅H₅)((R)–PROPHOS)(p-NCC₆H₄NO₂)][PF₆] ((R)–PROPHOS=(R)–(+)-bis-(1,2-diphenylphosphino)propane) were determined. A near-resonant enhanced β value as high as 545×10⁻³⁰ esu was obtained from hyper-Rayleigh scattering measurements. In addition, the compound crystallizes in the space group P1 with a perfect alignment of the dipolar molecules (only a single chromophore per unit cell), thus maximizing the macroscopic nonlinearity for electro-optic or parametric frequency conversion applications. The molecular packing in the crystal is analyzed in order to understand the factors leading to the perfect alignment.     

Reaction of Mo(CO)6 with Alkoxide: Synthesis and Structure of the Mo(0)-OR Complex [Et4N]3[Mo2(CO)6(μ-OC6H4OCH2C6H5)3]

The reaction of molybdenum hexacarbonyl with C6H5CH2OC6H4ONa and Et4NBr in CH3CN at 60 ℃ afforded the di-nuclear Mo(0) compound [Et4N]3[Mo2(CO)6(μ-OC6H4OCH2- C6H5)3] 1. 1 crystallizes in monoclinic, space group P21/c with a=15.359(2), b=18.378(3), c=24.952(2)(A), β=102.268(4)°, V=6882.3(16) (A)3, Mr=1348.34, Z=4, Dc=1.301 g/cm3, F(000)=2832 and μ= 0.424 mm-1. The final R=0.0606 and wR=0.1552 for 9396 observed reflections (Ⅰ ＞ 2σ(Ⅰ)). 1 contains a [Mo2O3]3- core in triangular bi-pyramidal configuration and each Mo atom adopts a distorted octahedral geometry with three carbon atoms from carbonyls and three μ-O atoms from C6H5CH2OC6H4O- bridging ligands. The Mo…Mo distance is 3.30(8) (A), indicating no metalmetal bonding. A formation pathway via forming a di-molybdenum(0) di-bridging OR compound [Mo2(μ-OR)2(CO)8]2- has been figured out and the reaction of Mo(CO)6 with alkoxide has also been discussed.     

Preparation and crystal structures of [μ-SbPh2]2[Mo(CO)2(η5-C5H5)]2·CHCl3 and SbPh[Fe(CO)2(η5-C5H5)]2

Antimony is reduced when [SbPh₂BrO]₂ is treated with Na[Mo(CO)₃(η⁵-C₅H₅)] to produce [μ-SbPh₂]₂[Mo(CO)₂(η⁵-C₅H₅)]₂. A structure determination shows diphenylstibido groups bridging between two Mo(CO)₂(η⁵-C₅H₅) moieties giving a central ‘butterfly’ shaped Sb₂Mo₂ ring. The cyclopentadiene rings are trans to each other and Mo–Sb and Sb–Sb separations are both short. An iron analogue could not be obtained from [SbPh₂BrO]₂ and Na[Fe(CO)₂(η⁵-C₅H₅)] but a mixture of SbPh[Fe(CO)₂(η⁵-C₅H₅)]₂ and SbPh₂[Fe(CO)₂(η⁵-C₅H₅)] was obtained using SbPh₂Cl. An X-ray structure for SbPh[Fe(CO)₂(η⁵-C₅H₅)]₂ shows an open stibinidine structure.     

REACTIONS OF [η5−RC5H4 (CO)2Mo]2 (Mo≡Mo) WITH (μ-PhSe)2Fe2 (CO)6. SYNTHESIS AND CHARACTERIZATION OF SELENOLATO-BRIDGED TRANSITION METAL COMPLEXES [η5−RC5H4Mo (CO) (μ-SePh)]2 (R ˭ MeCO,MeO2C) AND η5−RC5H4MoFe2 (CO)4 (μ3-Se) [μ,η1: η2−C(0)Ph] (μ-SePh)2 (R ˭ H,MeCO, EtO2C)

Abstract

Mo≡Mo triply bonded dimers [η⁵?RC₅H₄ —react with (μ,-PhSe)₂Fe₂ (CO)₆ in boiling xylene to give selenolato-bridged bimetallic complexes [η⁵?RC5H₄Mo(CO) (μ-SePh)]₂ (R ? MeCO, MeO₂C). However, irradiation of a benzene solution of —(R ? H, MeCO, EtO₂C) and (μ-PhSe)₂Fe₂ (CO)₆ with a 400W high pressure mercury lamp gave rise to selenolato-bridged trimetallic clusters η⁵?RC₅H₄MoFe₂(CO)₂ (μ₃-Se) [μ,η:η²?C (O) Ph] (μ-SePh)₂ (R ? H, MeCO, EtO₂C). All products were characterized by elemental analysis and spectroscopic methods, as well as by an X-ray diffraction analysis of the product η⁵?MeCOC₅H₄MoFe₂(CO)₄ (μ-Se)[μ;η¹:η²?C(O)Ph](μ-SePh)₂.     

Triethylaluminum-Based Ferrocenylalanes. Synthesis and Crystal Structure of (η5−C5H5)Fe[η5−C5H4Al2(C2H5)4Cl]

Abstract

The trietheylaluminum based ferrocenylalane (η⁵?C₅H₅)Fe[η⁵?C₅H₄Al₂(C₂H₅)₄Cl] was prepared from the reaction of triethylaluminum with chloromercuriferrocene in toluene and characterized by single crystal X-ray diffraction. The compound crystallizes in the triclinic space group P 1 with unit cell dimensions a = 9.353(3) Å, b = 10.281(7) Å, c = 11.599(9) Å, α = 79.64(7)°, β = 69.41(6)°, γ = 84.33(4)°, and Z = 2 for D_c = 1.27 g cm^?3. Full-matrix least-squares refinement has led to a final R factor of 0.068 based on 1866 independent observed reflections. The two diethylaluminum units are bridged by a chlorine atom and one carbon atom of a cyclopentadienyl group, thus forming an Al-Cl-Al-C ring. The four-membered ring is planar to within 0.02 Å. The Al-Cl distances are 2.404(4) Å and 2.266(5) Å. The Al-Cl-Al angle is 78.9(1)° while the Al-C-Al angle is 91.3(4)°. No significant aluminum-iron interaction is observed (Al… Fe = 3.137(4) Å).     

Molecular structure of ansa-compound (η5-C5H4)CMe2(η5-C9H6)TiCl2

The structure of a new ansa compound, (⁵-C₅H₄)CMe₂(⁵-C₉H₆)TiCl₂ (1), was studied by X-ray analysis:a = 15.00(1),b =15.500(5),c = 13.032(4) Å, = 92.66°(4),V = 3025.1(1) ų, space groupP2₁/.,R = 0.038. The distorted tetrahedral coordination sphere of the Ti atom is formed by two Cl atoms and two -ligands. It was proposed that the angle () between theC-M direction and the line normal to M-Cp can be considered as one of the geometric parameters characteristic of the structure-properties correlation.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 305–308, February, 1995.     

K4H2[SiW5Mo6Mn(H2O)O39]·22H2O的晶体结构

合成了一个锰硅钼钨四元取代含氧簇合物,用单晶X射线衍射方法测定了结构,该晶体属于四方晶系,空间群P4/mnc,a=14.119(3),c=12.496(4),V=2490.9(12)3,Mr=2862.70,z=2,Dc=3.817g*cm-3,μ=15.922mm-1,R=0.0462,wR=0.1232.锰硅钼钨阴离子中,中心SiO4四面体在C4轴的两个位置上是无序的.     

新型杂多蓝化合物[NH3(CH2)2NH3]5[Cd(H2O)][CdMoV12O30(HPO4)6(H2PO4)2]·5H2O的合成与晶体结构

利用水热法首次合成了具有两种配位环境Cd原子的新型杂多蓝化合物[NH3(CH2)2NH3]5[Cd(H2O)][CdMoV12O30(HPO4)6(H2PO4)2]·5H2O.通过元素分析、ICP、TG和X射线单晶衍射确定了其组成,使用IR和EPR进行了结构表征.通过N2吸附脱附测定了比表面积和孔径,为催化研究提供了基础数据.结果表明:该晶体为三斜晶系,P-1空间群;晶胞参数a=1.200 2(2)nm,b=1.465 1(3)nm,c=2.119 2(4)nm,V=3.5642(12)nm3,β=83.01(3)°,Z=2,F(000)=293 2,R1=0.0300,wR3=0.071 6.     

Synthesis and structures of the η5-C5H5Cl(CO)2W-η1,η5-(PPh2)C5H4(CO)2Fe-η1,η5-C5H4Mn(CO)3 and MeSi[C5H4(CO)2Fe-η1,η5-C5H4Mn(CO)2PPh3]3 complexes

The metallation of the η⁵-C₅H₅(CO)₂Fe-η¹,η⁵-C₅H₄Mn(CO)₃ complex with BuⁿLi (THF, ?78 °C) followed by the treatment of the lithium derivative with Ph₂PCl afforded the η⁵-Ph₂PC₅H₄(CO)₂Fe-η¹,η⁵-C₅H₄Mn(CO)₃ complex. The reaction of the latter with η⁵-C₅H₅(CO)₃WCl in the presence of Me₃NO produced the trinuclear complex η⁵-C₅H₅Cl(CO)₂W-η¹,η⁵-(Ph₂P)C₅H₄(CO)₂Fe-η¹,η⁵-C₅H₄Mn(CO)₃. The structure of the latter complex was established by IR, UV, and 1H and ³¹P NMR spectroscopy and X-ray diffraction. The reaction of MeSiCl₃ with three equivalents of LiC₅H₄(CO)₂Fe-η¹,η⁵-C₅H₄Mn(CO)₂PPh₃ gave the hexanuclear complex MeSi[C₅H₄(CO)₂Fe-η¹,η⁵-C₅H₄Mn(CO)₂PPh₃]₃.     

Synthesis,Crystal Structure and Vibrational Spectroscopy of NH4[Co(NH3)5(H2O)][B4O5(OH)4]2·6H2O

A novel hydrated cobalt tetraborate complex NH₄[Co(NH₃)₅(H₂O)][B₄O₅(OH)₄]₂·6H₂O, was synthesized by the reaction of NH₄‐borate aqueous with CoCl₂ and its structure was determined by single crystal X‐ray diffraction. The crystal system of this complex is orthorhombic, the space group is Pnma, and the unit cell parameters are a=1.2901(2) nm, b=1.6817(3) nm, c=1.1368(2) nm, α=β=γ=90°, V=2.4742(8) nm³, and Z=4. This compound contains infinite borate layers constructed from [B₄O₅(OH)₄]^2? units via hydrogen bonds. The adjacent polyborate anion layers are further linked together with the octahedral [Co(NH₃)₅(H₂O)]³⁺ groups through hydrogen bonds to form 3D framework. The groups and guest water molecules are deposited in the empty space of this framework and interact with the layers by extensive hydrogen bonds. Infrared and Raman spectra (4000–400 cm^?1) of NH₄[Co(NH₃)₅(H₂O)][B₄O₅(OH)₄]₂·6H₂O were recorded at room temperature and analyzed. Fundamental vibrational modes were identified and band assignments were made. The middle band observed at 575 cm^?1 in Raman spectrum is the pulse vibration of [B₄O₅(OH)₄]^2?.     

同多化合物[C6H5CH2NH(CH3)2]4[Mo8O26]·4H2O的合成与晶体结构

以MoO3和C6H5CH2N(CH3)2为原料,制得[C6H5CH2NH(CH3)2]4[Mo8O26]·4H2O,并通过扩散法得到无色透明晶体.X射线单晶衍射表明,晶体属三斜晶系,空间群为P墿,晶胞参数a=1.0685(2)nm,b=1.4050(3)nm,c=1.0643(2)nm,α=93.12(3)°,β=110.26(3)°,γ=71.41(3)°,V=1.4179(5)nm3,R=0.0383.     

DYNAMIC NMR STUDIES ON [Li(2D)][Nd(η~3-C_3H_5)_4]

The dynamic ~1H and ~(13)C-NMR studies on [Li(2D)][Nd(η~8-C_3H_5)_4](D=dioxane)were reported The four allyls coordinated to Hd~(8+) ion areequivalent and hydrogens appear as three groups in ~1H-NMR spectra with theirchemical shifts changing with temperature.C_1 and Ca are equivalent showing thecharacteristic of η~2=-allyl.The paramagnetic shifts of carbons in allylsinduced by Nd~(2+) ere separated sucessfully.C_1 and C_3 located on thezero-dipolar cone.The content of contact shift is greater than that of dipolarslift to Co.     

Regioselective permethylation,perallylation and perbenzylation of the arene ligand in [Ru(η5-C5Me5)(η6-C6Me6)][PF6]: a remarkable periodic effect

The reactions of [MCp^*(η⁶-C₆Me₆)][PF₆], M = Fe: 1, Ru: 2, Cp^* = η⁵-C₅Me₅, with KOH (in DME) or tert-BuOK (in THF) and methyl iodide, allyl bromide or benzyl bromide are regioselective on the arene ligand only for 2, giving the complexes [RuCp^*{η⁶-C₆(CH₂R)₆}][PF₆], R = methyl (3), allyl (4) or benzyl (5), although some formations of C-C bonds also occur on the Cp^* ligand in the case of the reactions of allyl and benzyl bromides. This contrasts with the complete lack of regioselectivity formerly observed with the iron analogue 1, and is best taken into account by the difference of steric effects which are less marked in 2 than in 1.     

Ditropylmolybdenum complexes by the sodium reduction of [Mo(CO)3(η-C7H7)][BF4]. X-Ray crystal structure of the ditropyl complex “Mo(CO)3”2(η6,η′6-C14H14)

Treatment of [Mo(CO)₃(η-C₇H₇)][BF₄] with either sodium amalgam or sodium naphthalide results in a reductive dimerisation to the ditropyl complex “Mo(CO)₃”₂(η₆,η′⁶-C₁₄H₁₄). The results of an X-ray crystallographic study confirm that the hydrogen atoms of the linking carbon atoms are both endo with respect to molybdenum. The reaction of Mo(CO)₆ with ditropyl, C₁₄H₁₄, leads to all three possible isomers of “Mo(CO)₃”²(η⁶,η′⁶-C₁₄-H₁₄). The structure of each is assigned by its ¹H NMR spectrum.     

Replacement of terminal and bridging oxo groups by phenylimido groups in (η-C5H5)OMo(μ-O)2OMo(η-C5H5) giving (η-C5H5)(NPh)Mo(μ-NPh)2Mo(NPh)(η-C5H5)

The treatment of (η-C₅H₅)OMo(μ-O)₂MoO(η-C₅H₅) with excess phenylisocyanate at reflux in tetrahydrofuran yields the arylimido-substituted complex (η-C₅H₅)(NPh)Mo(η-NPh)₂Mo(NPh)(η-C₅H₅), which has been characterized by elemental analysis, and mass, IR and ¹H NMR spectra.     

Synthesis, Characterization and Crystal Structure of [Co2Mo2(μ4-C2HPh)(μ-CO)4(CO)4(η5-C5H4C(O)Me)2]

The reaction of μ-alkyne-bridged dimolybdenum compound [Mo2(μ-C2HPh)(CO)4(η5-C5H4C(O)Me)2] 1 with Co2(CO)8 in refluxing toluene gave a new butterfly compound [Co2Mo2(μ4-C2HPh)(μ-CO)4(CO)4(η5-C5H4C(O)Me)2] 2 which was fully characterized by elemental analysis, IR, 1H NMR and X-ray single crystal diffraction techniques. 2 crystallized in monoclinic system, C30H20Co2Mo2O10, Mr=850.23, space group P21/a(#14), a=14.165(5), b=12.498(2), c=16.204(2)(A), β = 96.50(2)°, V = 2850(1)(A)3, Z = 4, Dc = 1.981 g cm-3, F(000)=1672, μ(MoKα)=20.41 cm-1, final R=0.030, Rw=0.039 for 4831 observable reflections with I>2σ(I). The structure contains a Co2Mo2 butterfly core, and each Mo-Co bond is spanned by an asymmetric semi-bridging carbonyl ligand.