Photochemical reactions of (CO)2 (PPh3)MnC5H4Fe(CO)2C5H5 and (CO)2(PPh3)MnC5H4COFe(CO)2C5H5 with PPh3

Conclusions The photochemical reactions of (CO)₂(PPh₃)MnC₅H₄Fe(CO)₂C₅H₅ and (CO)₂(PPh₃)MnC₅H₄COFe(CO)₂C₅H₅ with PPh₃ gave the products of replacing the CO on the Fe atom by PPh₃: respectively (CO)₂(PPh₃)MnC₅H₄Fe (CO)(PPh₃)C₅H₅ and (CO)₂(PPh₃)MnC₅H₄COFe(CO)(PPh₃)C₅H₅.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 12, pp. 2813–2815, December, 1977.     

Synthese und Kristallstruktur von (C5H5)Mo(CO)3(AuPPh3) und [(C5H5)Mo(CO)2(AuPPh3)4]PF6

Synthesis and Crystal Structure of (C₅H₅)Mo(CO)₃(AuPPh₃) and [(C₅H₅)Mo(CO)₂(AuPPh₃)₄]PF₆ CpMo(CO)₃(AuPPh₃) is obtained by the reaction of Li[CpMo(CO)₃] with Ph₃PAuCl at ?95°C in CH₂Cl₂. It crystallizes in the monoclinic space group C2/c with a = 2625.1(7), b = 883.2(1), c = 2328.4(7) pm, β = 116.39(1)° und Z = 8. In the complex the AuPPh₃ group is coordinated to the CpMo(CO)₃ fragment with a Au? Mo bond of 271,0 pm. The Mo atom thus achieves a square pyramidal coordination with the center of the Cp ring in apical position. CpMo(CO)₃(AuPPh₃) reacts under uv irradiation with an excess of Ph₃PAuN₃ to afford the cluster cation [CpMo(CO)₂(AuPPh₃)₄]⁺. It crystallizes as [CpMo(CO)₂(AuPPh₃)₄]PF₆ · 2 CH₂Cl₂ in the orthorhombic space group P2₁2₁2₁ with a = 1553.9(1), b = 1793.8(2), c = 2809.8(7) pm und Z = 4. The five metal atoms form a trigonal bipyramidal cluster skeleton with the Mo atom in equatorial position. The Mo? Au distances range from 275.5 to 280.8 pm, and the Au? Au distances are between 281.2 and 285.6 pm.     

Synthese und Eigenschaften der heteronuklearen Metallatomcluster Re4(CO)12[μ3-GaRe(CO)5]4 und Re2(CO)3[μ-GaRe(CO)5]2

Synthesis and Properties of Heteronuclear Metal Atom Clusters Re₄(CO)₁₂[μ₃-GaRe(CO)₅]₄ and Re₂(CO)₈[μ-GaRe(CO)₅]₂ The title compounds were prepared by the reaction of gallium halides and dirhenium decacarbonyl. Crystals of the four-membered cluster Re₂(CO)₈[μ-GaRe(CO)₅]₂ gave at 300⁰C with aggregation of four Re atoms to an inner Re₄ tetrahedron the product Re₄(CO)₁₂(CO)[μ₃-GaRe(CO)₅]₄and with Ga₂I₃ shown by mass spectroscopic measurements the molecule ion Re₄(CO)₁₆+. In tetra-hydrofuran solution the cluster Re₄(CO)₁₂[μ₃-GaRe(CO)₅]₄ and the hydride Li[C₂H₅)₃BH] have formed the formyl complex Li₄{Re₄(CO)₁₂[μ₃ -GaRe(CO)₄(CHO)] ₄}, which was estimated by ¹H n. m. r. and i. r. spectroscopic data. Both synthesized gallium rhenium carbonyl clusters were characterized by i.r. spectroscopic measurements. The comparison of these results with those of the structurally known indium rhenium carbonyl clusters led to proposals of the molecule structure of the analogous gallium rhenium compounds.     

Fluxional behavior of (CO)4Fe(u-AsMe2)Mo(CO)2(C5H5)

The ¹H and ¹³C NMR spectra of the heterobimetallic compound (CO)₄Fe(μ-AsMe₂)Mo(CO)₂(C₅H₅) reveal three different fluxional processes.     

Synthesis and Crystal Structure of (CO)5ReSnMe2Re(CO)5

１ＩＮＴＲＯＤＵＣＴＩＯＮＨｏｍｏ ｄｉｎｕｃｌｅａｒｍｅｔａｌｃａｒｂｏｎｙｌｃｌｕｓｔｅｒｓｈａｖｅｂｅｎｓｔｕｄｉｅｄｗｉｄｅｌｙｆｏｒｔｈｅｉｒｎｏｖｅｌｓｔｒｕｃｔｕｒｅｓａｎｄｕｓｅｓｉｎｏｒｇａｎｉｃｓｙｎｔｈｅｓｉｓ〔１〕．Ｅｘａｍｐ...     

Synthesis and structure of trinuclear clusters (Et4N)2[(μ3-Se)]Fe3(CO)9, [(μ-H)2Fe3(μ3-Se)(CO)9], and [(μ3-Se)FeMo2(η5-C5H5)2(CO)7]

The cluster anion [Fe₃(μ₃-Se)(CO)₉]^2- (I) was isolated as a salt (Et₄N)₂[I] by the reaction of Fe(CO)₅ with Na₂Se in isopropanol. The protonated form, (μ-H)₂Fe₃(μ₃-Se)(CO)₉ (II), was obtained by acidifying the reaction mixture and used for the synthesis of the heterometallic cluster FeMo₂(μ₃-Se)(CO)₇Cp₂ (III), CP=η⁵-C₅H₅. The structure of I and III was established by X-ray diffraction analysis. Crystals I are monoclinic, a=14.210(3), b=11.547(3), c=19.831(2), Å, β=90.92(2)°, V_cell=3254(1) ų, space group P2/c, Z=4, d_calc=1.550 g/cm³, Syntex P2₁, λCuK_α, R(F)=0.1333 for 1264 F_hkl>6σ(F_hkl). Crystals III are monoclinic, a=20.440(5), b=12.771(3), c=16.342(4) Å, β=113.80(2)°, V_cell=3903(2) ų, space group P2₁/c, Z=8, d_calc=2.222 g/cm³, Syntex P2₁, λCuK_α, R(F)=0.0734 for 1116 F_hkl>4σ(F_hkl). The structure of II was inferred from the Mössbauer, IR, and¹H and⁷⁷Se NMR spectroscopy data.     

Infrared study of some synthetic phases of malachite (Cu2(OH)2CO3)-hydrozincite (Zn5(OH)6(CO3)2) series

Synthetic malachite, hydrozincite and five monophasic mixed copper-zinc hydroxycarbonates have been studied by Fourier transform infrared (FTIR) spectroscopy at ambient and liquid nitrogen temperature in the region of 4000-400 cm(-1). The analysis of the spectra reveals that the samples containing up to 20% zinc retain the malachite lattice, thus forming solid solutions. The inclusion of zinc ions in malachite reflects on the positions and intensity of the bands corresponding to the internal modes of the carbonate ion, to the OH librations and to the Me-O interactions. For example, the higher and the lower frequency components of v3 shift to higher and lower frequencies, respectively. The intensity of the bands corresponding to v2 decreases with the zinc content increase. The spectrum of the sample Cu1.31Zn0.69(OH)2CO3 become diffuse and ill-resolved in the region of the Me-O interactions (region below 600 cm(-1)) and the corresponding bands are shifted to lower frequencies due to the weaker Zn-O interactions as compared with those of the copper ions. The internal modes of the carbonate ions in hydrozincite and aurichalcite are assigned and discussed taking into account the site symmetry and factor group symmetry. The OH and OD stretches (matrix-isolated HDO molecules) and the hydrogen bond strengths are interpreted in terms of Me-O interactions (synergetic effect), hydrogen bond angles and different hydrogen bond acceptor strengths of the oxygen atoms from the carbonate ions. It proves that the hydrogen bonds in hydrozincite are stronger as compared with those in malachite, irrespective of both the larger hydrogen bond lengths and the weaker Zn-O interactions in hydrozincite due to the higher hydrogen bond acceptor strength of the non-coordinated oxygen atom and the formation of bifurcated hydrogen bonds.     

Synthesis and characterization of complexes η5,η5-(CO)3Mn(C5H4-C5H4)(CO)2Fe-η1,η5-C5H4Mn(CO)3 and μ-(C≡C)[C5H4(CO)2Fe-η1,η5-C5H4Mn(CO)3]2

The complex η⁵,η⁵-(CO)₃Mn(C₅H₄-C₅H₄)(CO)₂Fe-η¹,η⁵-C₅H₄Mn(CO)₃ was synthesized by the reaction of η⁵-Cp(CO)₂Fe-η¹,η⁵-C₅H₄Mn(CO)₃ with BuⁿLi (THF, ?78 °C) and then with anhydrous CuCl₂. The complex μ-(C≡C)[C₅H₄(CO)₂Fe-η¹,η⁵-C₅H₄Mn(CO)₃]₂ was prepared by the reaction of η⁵-IC₅H₄(CO)₂Fe-η¹,η⁵-C₅H₄Mn(CO)₃ with Me₃SnC≡CSnMe₃ (2:1) in the presence of Pd(MeCN)₂Cl₂.