Multifunctional iron thiocarboxylate complexes: synthesis,reactivity and structure of CpFe(CO)<Subscript>2</Subscript>SCO-3,5-C<Subscript>6</Subscript>H<Subscript>4</Subscript>(COCl)<Subscript>2</Subscript>

A controlled substitution reaction of the chlorine atoms of 1,3,5-benzenetricarbonyl trichloride by the organoiron fragment (CpFe(CO)₂S) has been achieved. The complexes CpFe(CO)₂SCO-3,5-C₆H₃(COCl)₂ (1), 1,3-[CpFe(CO)₂SCO]₂-5-C₆H₃COCl (2) and 1,3,5-[CpFe(CO)₂SCO]₃C₆H₃ (3) were prepared from the reaction of (μ-S _x )[CpFe(CO)₂]₂ (x = 3, 4) with 1,3,5-C₆H₃(COCl)₃ in a 1:1, 2:1, or 3:1 metal to ligand molar ratio. The reactions of (1) with amines, thiols, and carboxylic acids produce the trifunctional mono-iron complexes CpFe(CO)₂SCO-3,5-C₆H₃(COY)₂ [Y = NR₂ (4), SR (5), OCOR (4)]. The X-ray structure determination of (1) is reported.     

The structure of monomeric unsolvated and weakly solvated (Me<Subscript>2</Subscript>Cu)Li and (Me<Subscript>2</Subscript>Cu)Cu

Density functional theory was used to study the structure of various isomers of (Me₂Cu)Li (1), (Me₂Cu)Cu (2), (Me₂Cu)Li · 2Me₂O (3), and (Me₂Cu)Cu · 2Me₂S (4) in the gas phase. Isomers of 1 and 3 were shown to be typical cuprates, whereas isomers of 2 and 4 should rather be treated as unsolvated and solvated methylcopper dimers, respectively. The reasons for the difference between structures 2, 4 and 1, 3 were considered. The energies of solvation of 1 by two dimethyl ether molecules (∼34 kcal/mol) and of 2 by two dimethyl sulfide molecules (∼36 kcal/mol) and the dissociation energies of all the compounds to the dimethylcuprate anion and the corresponding cation were calculated. The energies of solvation of 1 and 2 being almost equal, the transformation of 2 into 4 decreased the dissociation energy much more substantially than the transformation of 1 into 3.     

Arene complexes [(η-C<Subscript>5</Subscript>H<Subscript>5</Subscript>)M(η-C<Subscript>6</Subscript>R<Subscript>6</Subscript>)]<Superscript>2+</Superscript> (M = Rh,Ir)

The dicationic arene complexes [CpM(arene)](BF₄)₂ (arene = C₆H₆, 1,3,5-C₆H₃Me₃, or C₆Me₆) were synthesized by the reactions of the solvated complexes [CpM(MeNO₂)₃](BF₄)₂ (M = Rh, Ir) with benzene and its derivatives. The solvated complexes were generated in situ by abstraction of I^– from [CpMI₂]₂ with AgBF₄. A procedure was developed for the synthesis of the iodide [CpRhI₂]₂ based on the reaction of the cyclooctadiene derivative CpRh(1,5-C₈H₁₂) with I₂. The structure of the [CpRh(C₆Me₆)](BF₄)₂ complex was established by X-ray diffraction analysis.Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1871–1874, September, 2004.     

Synthesis and characterization of η<Superscript>3</Superscript>-allyl palladium(II) complexes with Ph<Subscript>2</Subscript>P(S)CHP(S)Ph<Subscript>2</Subscript> and OC(CF<Subscript>3</Subscript>)CHCO(C<Subscript>4</Subscript>H<Subscript>3</Subscript>S) co-ligands

The new complexes [(η³-Me₂CCMeCH₂)Pd{η²-Ph₂P(S)CHP(S)Ph₂] (1), [(η³-Me₂CCMeCH₂)Pd{η²-OC(CF₃) CHCO(C₄H₃S)}] (2) and [(η³-CH₂CMeCH₂)Pd{η²-OC(CF₃)CHCO(C₄H₃S)}] (3) have been synthesized by reacting [(η³-allyl)Pd(μ-Cl)]₂ with Ph₂P(S)CH₂P(S)Ph₂ and OC(CF₃)CH₂CO(C₄H₃S) in the presence of base. All have been characterized by elemental analysis, FT-IR, ¹H-n.m.r and FAB-mass spectroscopy. Spectroscopic studies suggest that both ligands are bidentate, forming six-membered Pd-S-P-C-P-S and Pd-O-C-C-C-O palladacycles, the η³-allyl group completing the coordination sphere.     

ESR Study of the Formation of O<Stack><Subscript>2</Subscript><Superscript>−</Superscript></Stack> Radical Anions on Oxidized CeO<Subscript>2</Subscript> and CeO<Subscript>2</Subscript>/ZrO<Subscript>2</Subscript> Adsorbing a CO + O<Subscript>2</Subscript> Mixture

It is demonstrated by ESR measurements that O ₂ ⁻ (CO + O₂) radical anions result from CO + O₂ adsorption on the oxidized surface of CeO₂. These radical anions are stabilized in the coordination sphere of Ce⁴⁺ cations located in isolated and associated anionic vacancies. This reaction shows an activation behavior determined by CO adsorption. The variation of O ₂ ⁻ (CO + O₂) concentration with CO adsorption temperature suggests that surface carbonates and carboxylates participate in this reaction. In the (0.5– 10.0)%CeO₂/ZrO₂ system, O ₂ ⁻ forms on supported CeO₂ and is stabilized on Ce⁴⁺ and Zr⁴⁺ cations. The stability of O ₂ ⁻ -Ce⁴⁺ complexes is lower on supported CeO₂ than on unsupported CeO₂, indicating a strong interaction between the cerium cations and the support.__________Translated from Kinetika i Kataliz, Vol. 46, No. 3, 2005, pp. 423–429.Original Russian Text Copyright © 2005 by Il’ichev, Kuli-zade, Korchak.     

Ruthenium Carbonyl Cluster Complexes with Phenylgermyl Ligands from the Reactions of Ph<Subscript>3</Subscript>GeH with Ru(CO)<Subscript>5</Subscript> and Ru<Subscript>3</Subscript>(CO)<Subscript>12</Subscript>

Four new triphenylgermylruthenium carbonyl compounds HRu(CO)₄GePh₃, 14; Ru(CO)₄(GePh₃)₂, 15; Ru₂(CO)₈(GePh₃)₂, 16; and Ru₃(CO)₉(GePh₃)₃(μ-H)₃, 17 were obtained from the reaction of Ru(CO)₅ with Ph₃GeH in hexane solvent at reflux, 68 °C. The major product 14 was formed by loss of CO from the Ru(CO)₅ and an oxidative addition of the GeH bond of the Ph₃GeH to the metal atom. This six coordinate complex contains one terminal hydrido ligand. Compound 15 is formed from 14 and contains two trans-positioned GePh₃ ligands in the six coordinate complex. Compound 16 contains two Ru(CO)₄(GePh₃) fragments joined by an Ru–Ru single bond. Compound 17 contains a triangular cluster of three ruthenium atoms with three bridging hydrido ligands and one terminal GePh₃ ligand on each metal atom. When heated to 125 °C, 14 was converted to the new triruthenium compound Ru₃(CO)₁₀(μ-GePh₂)₂, 18. Compound 18 consists of a triangular tri-ruthenium cluster with two GePh₂ ligands bridging two different edges of the cluster and one bridging CO ligand. Ru₃(CO)₁₂ was found to react with Ph₃GeH at 97 °C to yield three products: 15, and two new compounds Ru₃(CO)₉(μ-GePh₂)₃, 19 and Ru₂(CO)₆(μ-GePh₂)₂(GePh₃)₂, 20 were obtained. Compound 19 is similar to 18 having a triangular tri-ruthenium cluster but has three bridging GePh₂ ligands, one on each Ru–Ru bond. Compound 20 contains only two ruthenium atoms joined by a single Ru–Ru bond that has two bridging GePh₂ ligands and a terminal GePh₃ ligand on each metal atom. All compounds were characterized by a combination of IR, ¹H NMR, single-crystal X-ray diffraction analyses. This report is dedicated to Professor Dieter Fenske on the occasion of his 65th birthday for his many pioneering contributions to the chemistry of metal chalcogenide cluster complexes.     

Magnetic properties of a dinuclear complex (2,3-Me<Subscript>2</Subscript>C<Subscript>5</Subscript>H<Subscript>3</Subscript>N)<Subscript>2</Subscript>Fe<Subscript>2</Subscript>(μ-OOCCMe<Subscript>3</Subscript>)<Subscript>4</Subscript> with “China lantern” structure

Magnetic characteristics of the dinuclear complex (2,3-Me₂C₅H₃N)₂Fe₂(μ-OOCCMe₃)₄ (1) were studied in the temperature interval 2–300 K. The magnetic behavior of complex 1 was interpreted in terms of the orbital-dependent exchange theory with allowance for the temperature dependence of the populations of the split ⁵T_2g ground-state components of the Fe^II ions. The calculated values of the orbital-dependent exchange parameters are in good agreement with the results reported for dinuclear carboxylates of other 3d-transition metals and suggest the existence of strong ferromagnetism in some types of heterodinuclear carboxylates.__________Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 2035–2039, October, 2004.     

Reactions of (dpp-BIAN)Mg(thf)<Subscript>3</Subscript> complex (dpp-BIAN is 1,2-bis{(2,6-diisopropylphenyl)imino}acenaphthene) with halogen-containing reagents

The reactions of the acenaphthenediimine complex (dpp-BIAN)Mg(thf)₃ (1) (dpp-BIAN is 1,2-bis{ (2,6-diisopropylphenyl)imino}acenaphthene) with various chlorine-, bromine-, and iodine-containing reagents afforded the unsymmetrical compounds [(dpp-BIAN)MgCl(thf)]₂ (6), [(dpp-BIAN)MgBr(thf)]₂ (7), and (dpp-BIAN)MgI(DME) (8). The reaction of complex 1 with Me₃SiCl in THF is accompanied by the cleavage of the THF molecule to form [{dpp-BIAN(CH₂)₄OSiMe₃}MgCl]₂ (9), in which the trimethylsilanyloxybutyl group is bound to one of the carbon atoms of the diimine fragment. The reaction of complex 1 with Me₂NCH₂CH₂Cl in THF produces the [dpp-BIAN(H)(CH₂)₂NMe₂] compound (10) containing no magnesium. Paramagnetic complexes 6–8 were characterized by ESR spectroscopy. Diamagnetic compounds 9 and 10 were studied by ¹H and ¹³C NMR spectroscopy. The molecular structures of complexes 6–10 were established by X-ray diffraction analysis. In the crystalline state, compounds 6, 7, and 9 exist as halogen-bridged dimers. In all magnesium derivatives, BIAN serves as a chelate ligand.__________Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 12, pp. 2641–2651, December, 2004.     

Reaction of the novel Ru<Subscript>3</Subscript>(CO)<Subscript>10</Subscript>[Ph<Subscript>2</Subscript>P(CH<Subscript>2</Subscript>)<Subscript>2</Subscript>Si(OEt<Subscript>3</Subscript>)]<Subscript>2</Subscript> complex on SBA-15 and MCM-41 mesoporous silicas

The reaction of Ru₃(CO)₁₂ with 2(diphenylphosphino)ethyl-triethoxysilane (DPTS) in hydrocarbons, leads to the functionalized Ru₃(CO)_12−n [Ph₂P(CH₂)₂Si(OEt₃)] _n (n = 1,2) complexes. The complex with two phosphine substituents was chemically anchored on mesoporous silicas, SBA-15 and MCM-41, in order to obtain two hybrid materials characterized by a different localization of the metal centre on the surface of the porous supports. A detailed investigation of the cluster, before and after chemical anchoring on the mesoporous silicas, was pursued. Particular attention was also devoted to the study of the morphological, structural and textural properties of the metal-functionalised silicas (Ru/SBA-15 and Ru/MCM-41) by infrared spectroscopy (FT-IR), scanning electron microscopy, X-ray diffraction and N₂ physisorption analysis.     

Specific features of the thermodynamics of activation in the LaNi<Subscript>5</Subscript>-H<Subscript>2</Subscript> and CeNi<Subscript>5</Subscript>-H<Subscript>2</Subscript> systems

Using heat conducting Tian—Calvet calorimetry and volumetric measurements, the first hydrogen absorption—desorption cycles in the LaNi₅-H₂ and CeNi₅-H₂ systems were studied. The pressure—composition isotherms were plotted, the equilibrium pressures of hydrogen along the absorption and desorption branches and in the region of hysteresis for different activation steps were determined, and the enthalpies of phase transitions α → β and β → α were calculated. The profiles of the heat evolution curves were analyzed. It was concluded that the mechanism of the reactions studied changes upon activation.__________Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 134–139, January, 2005.     

Adsorption of water isotopomers H<Subscript>2</Subscript>O and D<Subscript>2</Subscript>O on hypercross-linked polystyrene MN-272

Adsorption of light and heavy water (H₂O and D₂O) on porous hypercross-linked polystyrene MN-272 was studied by gas chromatography. For the estimation of the properties of this polymer surface, n-alkanes (C6—C9), C_{6 6}, and polar compounds (CHCl₃, MeNO₂, MeCN, Me₂CO, EtCOOCH₃, Et₂O) were used as test adsorbates. The contributions of energies of dispersion and specific (donor-acceptor) intermolecular interactions to the total energy of adsorption were determined on the basis of experimental data on the retention of the sorbates. The electron-donor and electron-acceptor characteristics of the hypercross-linked polystyrene MN-272 surface were estimated. Hypercross-linked polystyrene MN-272 was found to be a weakly specific adsorbent with predomination of electron-donating properties. The adsorption isotherms of H₂O and D₂O were measured on this polymer at 50, 60, and 70 °C. The dependences of the isosteric heats of adsorption on the amount adsorbed were determined. The contribution of the energy of specific interactions to the total energy of adsorption for all polar adsorbates (except for acetone, light and heavy water) does not exceed 20%. Adsorption of H₂O on hypercross -linked polystyrene MN-272 is slightly weaker than that of D ₂O.     

(Tetramethylcyclobutadiene)cobalt complexes 7. Mono- and dinuclear arene complexes containing the [(C<Subscript>4</Subscript>Me<Subscript>4</Subscript>)Co]<Superscript>+</Superscript> fragment

The mononuclear arene complexes [Cb*Co(arene)]⁺ (3a–g; Cb* = C₄Me₄; arene is biphenyl (a), diphenylmethane (b), 1,2-diphenylethane (c), diphenyl ether (d), p-terphenyl (e), 1,2-dimesitylethane (f), or 1,3-dimesitylpropane (g)) were synthesized by the reactions of arenes either with the benzene complex [Cb*Co(C₆H₆)]⁺ (1) under visible light irradiation or with the acetonitrile derivative [Cb*Co(MeCN)₃]⁺ (2) in refluxing THF. The reactions of 2 with 1,2-diphenyle-thane, 1,3-dimesitylpropane, and p-terphenyl in a ratio of 2: 1 afforded the dinuclear complexes [Cb*Co(μ-η:η-arene)CoCb*]²⁺ (4c,e,g). The stability of the dinuclear arene complexes was estimated by DFT calculations. The structures of the complexes [3a]PF₆ and [3e]PF₆ ere established by X-ray diffraction. For Part 6, see Ref. 1. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 535–539, March, 2008.     

Photochemical reactions of <Emphasis Type="Italic">cis</Emphasis>-[(η<Superscript>4</Superscript>-NBD)M(CO)<Subscript>4</Subscript>] (NBD = norbornadiene; M = Cr,Mo) olefin complex with ligand,containing S and N donor atoms

New complexes cis-[M(CO)₄-DABRd] (M = Cr(I), Mo(II) and fac-[M(CO)₃-SAT] (M = Cr(III), Mo(IV)) have been synthesized by the photochemical reactions of cis-[(η⁴-NBD)M(CO)₄] (NBD is norbornadiene; M=Cr, Mo) with 5-(4-dimethylaminobenzylidene) rhodanine (DABRd) and salicylidene-3-amino-1,2,4-triazole (SAT) ligands and characterized by elemental analysis, FT-IR and ¹H NMR spectroscopy, and mass spectrometry. The spectroscopic studies show that the DABRd ligand acts as a bidentate ligand coordinating via both NH-(S)C=S sulfur donor atoms in I and II and SAT ligand behaves as a tridentate ligand coordinating via its all imine nitrogen-C=N-donor atoms in III and IV to the metal center. The article was submitted by the authors in English.     

Thermal study of cyclopalladated complexes of the type [Pd<Subscript>2</Subscript>(dmba)<Subscript>2</Subscript>X<Subscript>2</Subscript>(bpe)]

The synthesis, characterization and thermal analysis of the novel cyclometallated compounds [Pd₂(dmba)₂Cl₂(μ-bpe)] (1), [Pd₂(dmba)₂(N₃)₂(μ-bpe)] (2), [Pd₂(dmba)₂(NCO)₂(μ-bpe)] (3), [Pd₂(dmba)₂(SCN)₂(μ-bpe)] (4), [Pd₂(dmba)₂(NO₃)₂(μ-bpe)] (5) (bpe=trans-1,2-bis(4-pyridyl)ethylene; dmba=N,N-dimethylbenzylamine) are described. The thermal stability of [Pd₂(dmba)₂X₂(μ-bpe)] complexes varies in the sequence 1>4>3>2>5. The final residues of the thermal decompositions were characterized as metallic palladium by X-ray powder diffraction.     

Reactivity of triangular oxalate cluster complexes [M<Subscript>3</Subscript>Q<Subscript>7</Subscript>(C<Subscript>2</Subscript>O<Subscript>4</Subscript>)<Subscript>3</Subscript>]<Superscript>2−</Superscript> (M = Mo or W; Q = S or Se)

The reactions of the oxalate complexes [M₃Q₇(C₂O₄)₃]²⁻ (M = Mo or W; Q = S or Se) with Mn^II, Co^II, Ni^II, and Cu^II aqua and ethylenediamine complexes in aqueous and aqueous ethanolic solutions were studied. The previously unknown heterometallic complexes [Mo₃Se₇(C₂O₄)₃Ni(H₂O)₅]·3.5H₂O (1) and K₃{[Cu(en)₂H₂O]([Mo₃S₇(ox)₃]₂Br)}·5.5H₂O (2) were synthesized. In these complexes, the oxalate clusters serve as monodentate ligands. The K(H₂en)₂[W₃S₇(C₂O₄)₃]₂Br·4H₂O salt (3) was isolated from solutions containing Co^II, Ni^II, or Cu^II aqua complexes and ethylenediamine. The reaction of [Mo₃Se₇(C₂O₄)₃]²⁻ with HBr produced the bromide complex [Mo₃Se₇Br₆]²⁻, which was isolated as (Bu₄N)₂[Mo₃Se₇Br₆] (4). Complexes 1–3 were characterized by X-ray diffraction, IR spectra, and elemental analysis. The formation of 4 was detected by electrospray mass spectrometry. Dedicated to Academician G. A. Abakumov on the occasion of his 70th birthday. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1645–1649, September, 2007.     

Synthesis of cationic complexes [(C<Subscript>4</Subscript>Me<Subscript>4</Subscript>)CoL]<Superscript>+</Superscript> (L is naphthalene,phenanthrene, and anthracene)

Cationic arene complexes [Cb*Co(naphthalene)]⁺ (2, Cb* = C₄Me₄) and [Cb*Co(phenanthrene)]⁺ were synthesized by the reactions of [Cb*Co(MeCN)₃]⁺ with arenes. The [Cb*Co(anthracene)]⁺ complex was synthesized by the abstraction of the iodide ion from [Cb*CoI]₂ by TIBF₄ in the presence of anthracene. Complex 2 exchanges the naphthalene ligand for other arenes at room temperature. Dedicated to Academician G. A. Abakumov on the occasion of his 70th birthday. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1861–1863, September, 2007.     

Replacement of Fe atoms by Ru in a carbidocarbonyl cluster [Fe<Subscript>6</Subscript>C(CO)<Subscript>16</Subscript>]<Superscript>2−</Superscript>. Structures of reaction products

The reaction of the carbidocarbonyl cluster [Fe₆C(CO)₁₆]²⁻ with ruthenium(IV) hydroxochloride Ru(OH)Cl₃ was studied. At 90–100 °C, the reaction gave products of replacement of Fe atoms by Ru in the [Fe₆C(CO)₁₆]²⁻ cluster along with degradation products. Treatment of the replacement products with FeCl₃ afforded the [Fe_2.96Ru_3.04C(CO)₁₇] compound (1), which was characterized by X-ray diffraction analysis. The crystals of cluster 1 are composed of two types of octahedral molecules (1a and 1b) in a ratio of 2 : 1. Molecules 1a are in general positions, and molecules 1b are located on twofold axes. In both molecules, the Fe and Ru atoms are disordered over four of six positions. __________ Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1761–1766, August, 2005.     

Synthesis,Structure and Isomerism of the [Fe<Subscript>3</Subscript>Pt(μ<Subscript>4</Subscript>-Q)(CO)<Subscript>9</Subscript>(dppm)] Clusters (Q = Se,Te; dppm = Ph<Subscript>2</Subscript>PCH<Subscript>2</Subscript>PPh<Subscript>2</Subscript>)

The reaction of K₂[Fe₃(μ₃-Q)(CO)₉] (Q = Se (K₂[1a]), Te (K₂[1b])) with [(dppm)PtCl₂] leads to the addition of a [(dppm)Pt]²⁺ unit to a Fe₂Q face of the initial cluster. By this way new heteronuclear clusters [Fe₃Pt(μ₃-Q)(CO)₉(dppm)] were obtained possessing a butterfly-shaped cluster core bridged by a μ₄-Q unit. It has been found that the resulting Fe-Pt clusters exist as equilibrium mixtures of two isomeric forms in solution differing by the dppm coordination mode: as a chelate ligand coordinated to Pt or as a bridging ligand coordinated to Pt and Fe atoms. The mixtures of isomers can be separated by chromatography and the pure isomers can be isolated as stable crystalline phases. Solutions of both isomers attain equilibrium at normal conditions in about 1 month as found by NMR. Dedicated to Professor Dieter Fenske in the occasion of his 65th birthday.     

Synthesis and Structure of the Copper(II) Complex with <Emphasis Type="Italic">ortho</Emphasis>-Phthalic Acid and 1-Methylimidazole [Cu(HPht)<Subscript>2</Subscript>(1-CH<Subscript>3</Subscript>Im)<Subscript>2</Subscript>]

A new Cu(II) complex [Cu(HPht)₂(1-CH₃Im)₂] (I), where HPht is the monoanion of o-phthalic acid and 1-CH₃Im is 1-methylimidazole, is synthesized and characterized by IR spectroscopy, thermogravimetry, and X-ray diffraction analysis. Compound I contains molecular complexes in which the o-phthalic acid residue is monodeprotonated and linked to a metal through the carboxyl group in a 1,3-chelate mode. The cis-octahedral coordination of copper is formed by two HPht residues and two 1-CH₃Im molecules. The distances are Cu-N1.945(6) Å, Cu-O2.018(5) Å and 2.374(6) Å. Polymeric chains are formed in complex I due to intermolecular hydrogen bonds. The chains are unified into layers by the interactions between the 1-CH₃Im molecules of the adjacent complexes.__________Translated from Koordinatsionnaya Khimiya, Vol. 31, No. 8, 2005, pp. 630–635.Original Russian Text Copyright © 2005 by Gherco.     

Synthesis,characterization and olefin hydroformylation reactions of <Emphasis Type="Italic">mer</Emphasis>-[Mo(CO)<Subscript>3</Subscript>(p-C<Subscript>5</Subscript>H<Subscript>4</Subscript>N-CN)<Subscript>3</Subscript>]

Mer-[Mo(CO)₃(p-C₅H₄N-CN)₃] was prepared by UV-irradiation of a THF solution of Mo(CO)₆ and para-cyanopyridine under heating. The complex was characterized by FT-IR, MS, ¹H and ¹³C NMR and showed catalytic activity for olefin hydroformylation (1-hexene, cyclohexene and 2,3-dimethyl-2-butene as model olefins; 600 psi synthesis gas (pCO/pH₂ = 1); 100 °C; 24 h; toluene). An examination of the complex catalyzed hydroformylation of a real naphtha cut (El Palito refinery, Venezuela), under the same conditions, also showed activity in the conversion to oxygenated products.