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.     

A new reaction of [Cp((CO)2Fe(PPh2H)]PF6 with NaBH4 to give Cp(CO)(H)Fe(PPh2H) via Cp(CO)2FeH and PPh2H

[Cp((CO)₂Fe(PPh₂H)]PF₆ reacts with NaBH₄ to give the intermediates CpFe(CO)₂H and PPh₂H, which are then converted into Cp(CO)(H)Fe(PPh₂H). [Cp(CO)₂FeL]PF₆ (L = P(OMe)₃, P(OEt)₃ and P(OⁱPr)₃) reacts with NaBH₄ to give the product Cp(CO)(H)FeL directly without Cp(CO)₂FeH and L even being formed transiently. The proposed reaction mechanism is that H⁻ attacks th phosphorus atom to give a metallaphosphorane complex, followed by coupling between a Cp(CO)₂Fe fragment and H on the hypervalent phosphorus.     

Reaction of bis(phosphine)(hydrotris(3,5-dimethylpyrazolyl)borato)rhodium(I) with phenylacetylene,p-nitrobenzaldehyde,and triphenyltin hydride: structures of [Rh(Tp)(PPh(3))(2)], [Rh(Tp)(H)(C(2)Ph)(P(4-C(6)H(4)F)(3))], [Rh(Tp)(H)(COC(6)H(4)-4-NO(2))(PPh(3))], and [Rh(Tp)(H)(SnPh(3))(PPh(3))

The complexes [Rh(Tp)(PPh(3))(2)] (1a) and [Rh(Tp)(P(4-C(6)H(4)F)(3))(2)] (1b) combine with PhC(2)H, 4-NO(2)-C(6)H(4)CHO and Ph(3)SnH to give [Rh(Tp)(H)(C(2)Ph)(PR(3))] (R = Ph, 2a; R = 4-C(6)H(4)F, 2b), [Rh(Tp)(H)(COC(6)H(4)-4-NO(2))(PR(3))] (R = Ph, 3a), and [Rh(Tp)(H)(SnPh(3))(PR(3))] (R = Ph, 4a; R = 4-C(6)H(4)F, 4b) in moderate to good yield. Complexes 1a, 2b, 3a, and 4a have been structurally characterized. In 1a the Tp ligand is bidentate, in 2b, 3a, and 4a it is tridentate. Crystal data for 1a: space group P2(1)/c; a = 11.9664(19), b = 21.355(3), c = 20.685(3) A; beta = 112.576(7) degrees; V = 4880.8(12) A(3); Z = 4; R = 0.0441. Data for 2b: space group P(-)1; a = 10.130(3), b = 12.869(4), c = 17.038(5) A; alpha = 78.641(6), beta = 76.040(5), gamma = 81.210(6) degrees; V = 2100.3(11) A(3); Z = 2; R = 0.0493. Data for 3a: space group P(-)1; a = 10.0073(11), b = 10.5116(12), c = 19.874(2) A; alpha = 83.728(2), beta = 88.759(2), gamma = 65.756(2) degrees; V =1894.2(4) A(3); Z = 2; R = 0.0253. Data for 4a: space group P2(1)/c; a = 15.545(2), b = 18.110(2), c = 17.810(2) A; beta = 95.094(3) degrees; V = 4994.1(10) A(3); Z = 4; R = 0.0256. NMR data ((1)H, (31)P, (103)Rh, (119)Sn) are also reported.     

Synthesis of RuH2(CO)(PPh3)3 in a CO2 and H2 atmosphere

Summary RuH₂(CO)(PPh₃)₃ was prepared in a CO₂ and H₂ atmosphere from RuCl₃ and PPh₃ in the presence of alcohol and Et₃N. Introduction of CO into the system lead to the formation of other complexes e.g. Ru(CO)₃-(PPh₃)₂. Addition of alkali in place of Et₃N resulted in a decrease in the RuH₂(CO)(PPh₃)₃ yield.Author to whom all correspondence should be directed.     

A novel class of aryldiazene complexes: [(PPh3)2 (CO)IrCl(HNNC6H4R-p)(CCPh)] (BF4) (R = NO2, CN,COCH3)

In the reaction with phenylacetylene leading to [(PPh₃)₂(CO)IrCl (HNNC₆H₄R-p)(CCPh)] (BF₄) (R  NO₂, CN, COCH₃), the vacant coordination site in [(PPh₃)₂ (CO)IrCl(N₂C₆H₄ R-p)] (BF₄) plays a key role in the activation of the acetylenic CH bond. ca]To whom correspondence should be addressed.     

Synthesis,Characterization, and X‐ray Structures of Ru3(CO)9(dotpm)(L) Complexes [L = PPh3, P(C6H4Cl‐p)3, and PPh2(C6H4Br‐p)]

The reaction of Ru₃(CO)₁₀(dotpm) ( 1 ) [dotpm = (bis(di‐ortho‐tolylphosphanyl)methane)] and one equivalent of L [L = PPh₃, P(C₆H₄Cl‐p)₃ and PPh₂(C₆H₄Br‐p)] in refluxing n‐hexane afforded a series of derivatives [Ru₃(CO)₉(dotpm)L] ( 2 – 4 ), respectively, in ca. 67–70 % yield. Complexes 2 – 4 were characterized by elemental analysis (CHN), IR, ¹H NMR, ¹³C{¹H} NMR and ³¹P{¹H} NMR spectroscopy. The molecular structures of 2 , 3 , and 4 were established by single‐crystal X‐ray diffraction. The bidentate dotpm and monodentate phosphine ligands occupy equatorial positions with respect to the Ru triangle. The effect of substitution resulted in significant differences in the Ru–Ru and Ru–P bond lengths.     

The syntheses,crystal, molecular and electronic structures of two polymorphs of [ReCl2(N2COPh)(C3N2H4)(PPh3)2] and [ReCl2(N2COPh)(py)(PPh3)2] complexes

The [ReCl₂(η²-N₂COPh–N^′,O)(PPh₃)₂] complex reacts with pyridine and pyrazole to give [ReCl₂(N₂COPh)(py)(PPh₃)₂] and [ReCl₂(N₂COPh)(C₃N₂H₄)(PPh₃)₂], respectively. Two monoclinic polymers of [ReCl₂(N₂COPh)(C₃N₂H₄)(PPh₃)₂] and [ReCl₂(N₂COPh)(py)(PPh₃)₂] have been characterized by IR, UV–Vis, ¹H NMR, magnetic measurements and X-ray structure.     

ESR study of radical adducts of dialkoxyphosphoryl radicals with (η2-C60)lrH(CO)(PPh3)2 and (η2-C60IrH(8H12)(PPh3)

The reaction of phosphoryl radicals with (η²-C₆₀)lrH(CO)(PPh₃)₂ and (η²-C₆₀IrH(₈H₁₂)(PPh₃) was shown (ESR) to result in the formation of isomers differing in the constants of hyperfine interaction (HFI) with³¹P nuclei,g-factors, and linewidths. It is likely that the addition of phosphoryl radicals at a distance of two-three bond lengths from the metallofragment is predominant. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 4, pp. 870–872, April, 1997.     

Crystal structure and luminescence of lanthanide monodentate complexes [Ln(C(4)N(4)H(6)O)(2)(H(2)O)(6)]Cl(3) and [Ln(C(4)N(4)H(6)O)(2)(H(2)O)(3)(NO(3))(3)] (Ln = Tb or Eu)

New eight- and nine-coordinate luminescent europium(III) and terbium(III) complexes 1-4 with carbonyl group coordination have been prepared using the monodentate ligand (L) 2,4-diamino-6-hydroxy pyrimidine and characterized by X-ray and spectroscopic methods.     

NMR studies of Ru(3)(CO)(10)(PMe(2)Ph)(2) and Ru(3)(CO)(10)(PPh(3))(2) and their H(2) addition products: detection of new isomers with complex dynamic behavior

The clusters Ru(3)(CO)(10)L(2), where L = PMe(2)Ph or PPh(3), are shown by NMR spectroscopy to exist in solution in at least three isomeric forms, one with both phosphines in the equatorial plane on the same ruthenium center and the others with phosphines in the equatorial plane on different ruthenium centers. Isomer interconversion for Ru(3)(CO)(10)(PMe(2)Ph)(2) is highly solvent dependent, with DeltaH decreasing and DeltaS becoming more negative as the polarity of the solvent increases. The stabilities of the isomers and their rates of interconversion depend on the phosphine ligand. A mechanism that accounts for isomer interchange involving Ru-Ru bond heterolysis is suggested. The products of the reaction of Ru(3)(CO)(10)L(2) with hydrogen have been monitored by NMR spectroscopy via normal and para hydrogen-enhanced methods. Two hydrogen addition products are observed with each containing one bridging and one terminal hydride ligand. EXSY spectroscopy reveals that both intra- and interisomer hydride exchange occurs on the NMR time scale. On the basis of the evidence available, mechanisms for hydride interchange involving Ru-Ru bond heterolysis and CO loss are proposed.     

Synthesis,molecular and electronic structure of [ReCl2(N2COPh)(C4N2H4)(PPh3)2]

A new organodiazenido rhenium complex, [ReCl₂(N₂COPh)(C₄N₂H₄)(PPh₃)₂] has been obtained from the direct reaction of [ReCl₂(η²–N₂COPh–N′,O)(PPh₃)₂] with pyrazine in acetone. The complex has been characterized by spectroscopic methods and its structure determined using single-crystal X-ray diffraction techniques.     

Addition of C2(CO2Me)2 to trans-MeIr(CO)(PPh3)2. Formation and isomerization of MeIr(CO)(PPh3)2[C2(CO2Me)2], and crystal structure of the thermodynamic isomer

The reaction of C₂(CO₂Me)₂ with trans-MeIr(CO)(PPh₃)₂ leads to a kinetic isomer which has been characterized by ¹H and ³¹P NMR and infrared spectra and to a thermodynamic isomer which has been characterized by ¹H and ³¹P NMR, infrared, microanalysis and X-ray crystallography. The isomerization occurs readily in solution at room temperature; somewhat more slowly at −20°C. The thermodynamically stable isomer of MeIr(CO)(PPh₃)₂[C₂(CO₂Me)₂] crystallizes in the centrosymmetric monoclinic space group P2₁/c with a 14.847(2), b 16.648(2), c 15.656(3) Å, β 90.595(14)°, V 3869.7(11) ų and Z = 4. Single-crystal X-ray diffraction data were collected with a Syntex P2₁ automated diffractometer (Mo-K_α radiation, 2θ 5–40°) and the structure was solved and refined to R_F 8.6% for all 3631 independent data (R_F 4.0% for those 2318 data with |F_o| > 6σ(|F_o|)). The Ir^I center has a trigonal-bipyramidal environment with the methyl ligand and one PPh₃ ligand occupying axial sites (Ir-Me 2.193(14), Ir-P(1) 2.425(4) Å). The C₂(CO₂Me)₂ ligand is π-bonded to the iridium atom and lies with its triple bond parallel to the equatorial coordination plane; the equatorial ligands are completed by the second PPh₃ ligand (Ir-P(2) 2.402(3) Å) and a CO ligand (Ir-CO 1.812(15) Å).     

Synthesis of low-valent thiocarbonyl complexes via 1,2-elimination of methylthiol from cis-metal-hydrido-dithiomethylester complexes. Os(cs)(CO)2(PPh3)2 and IrCl(CS)(PPh3)2.

[OS(η²-CS₂Me)(CO)₂(PPH₃)₂]⁺ and [Ir(η²-CS₂Me)Cl(CO)(PPh₃)₂)⁺ react with NaBH₄ giving OsH(CS₂Me)(CO)₂(PPh₃)₂ and IrH(CS₂Me)Cl(CO)(PPh₃)₂ respectively; These compounds contain mutually $\text{cis}$ hydride and η¹-dithiomethylester ligands and upon heating undergo 1,2-elimination of MeSH producing Os(CS)(CO)₂(PPh₃)₂ and IrCl(CS)(PPh₃)₂.     

Thermodynamic hydride donor abilities of [HW(CO)4L]- complexes (L = PPh3, P(OMe)3, CO) and their reactions with [C5Me5Re(PMe3)(NO)(CO)]+

The thermodynamic hydride donor abilities of [HW(CO)(5)](-) (40 kcal/mol), [HW(CO)(4)P(OMe(3))](-) (37 kcal/mol), and [HW(CO)(4)(PPh(3))](-) (36 kcal/mol) have been measured in acetonitrile by either equilibrium or calorimetric methods. The hydride donor abilities of these complexes are compared with other complexes for which similar thermodynamic measurements have been made. [HW(CO)(5)](-), [HW(CO)(4)P(OMe(3))](-), and [HW(CO)(4)(PPh(3))](-) all react rapidly with [CpRe(PMe(3))(NO)(CO)](+) to form dinuclear intermediates with bridging formyl ligands. These intermediates slowly form [CpRe(PMe(3))(NO)(CHO)] and [W(CO)(4)(L)(CH(3)CN)]. The structure of cis-[HW(CO)(4)(PPh(3))](-) has been determined and has the expected octahedral structure. The hydride ligand bends away from the CO ligand trans to PPh(3) and toward PPh(3).     

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.