Synthesis, crystal, molecular, and electronic structures of hydride carbonyl ruthenium(II) complexes with pseudohalide ligands

Two pseudohalide hydride carbonyl ruthenium(II) complexes with formulae: [RuH(N₃)(CO)(PPh₃)₃] (1) and [RuH(NCO)(CO)(PPh₃)₃] (2) have been synthesized by the reactions of [RuHCl(CO)(PPh₃)₃] with sodium azide or sodium cyanate, respectively, and are compared with the previously described thiocyanate analog [RuH(NCS)(CO)(PPh₃)₃]. The molecular structures of the new compounds were determined by X-ray crystallography and their spectroscopic properties have been studied. Based on the crystal structures, computational investigations have been carried out in order to determine the electronic structures of the complexes. The electronic spectra were calculated with the use of time-dependent DFT methods, and the electronic spectra of the transitions were correlated with the molecular orbitals of the complexes.     

Ir(I)–carbonyl complexes of coumarinazoimidazoles: Synthesis structure, electrochemistry, photophysical properties and DFT calculations

The reactions of Vaska’s complex [IrCl(CO)(PPh₃)₂] with 2-(coumaryl-6-azo)imidazole (CZ-H) and its derivatives (CZ-X) have synthesized [Ir(CZ)(CO)(PPh₃)₂] and [Ir(CZ-X)(CO)(PPh₃)₂]. All the complexes have been characterized by FT-IR, UV-Vis, ¹H NMR and FAB-MS spectroscopy. The structural confirmation has been done in one case, by a single crystal X-ray diffraction study, which shows a distorted square pyramidal geometry around the central Ir atom. The complexes are emissive at room temperature. The cyclic voltammetry of the complexes shows a metal centered irreversible oxidation and ligand centered quasireversible reduction couples. To get an insight into the electronic structure, absorption spectra and electrochemical properties, detailed calculations on all three complexes have been performed at the DFT level.     

Synthesis, structure, spectroscopic properties, electrochemistry, and DFT correlative studies of N-[(2-pyridyl)methyliden]-6-coumarin complexes of Cu(I) and Ag(I)

6-Aminocoumarin reacts with pyridine-2-carboxaldehyde and has synthesized N-[(2-pyridyl)methyliden]-6-coumarin (L). The ligand, L, reacts with [Cu(MeCN)₄]ClO₄/AgNO₃ to synthesize Cu(I) and Ag(I) complexes of formulae, [Cu(L)₂]ClO₄ and [Ag(L)₂]NO₃, respectively. While similar reaction in the presence of PPh₃ has isolated [Cu(L)(PPh₃)₂]ClO₄ and [Ag(L)(PPh₃)₂]NO₃. All these compounds are characterized by FTIR, UV-Vis and ¹H NMR spectroscopic data. In case of [Cu(L)(PPh₃)₂]ClO₄ and [Ag(L)(PPh₃)₂]NO₃, the structures have been confirmed by X-ray crystallography. The structure of the complexes are distorted tetrahedral in which L coordinates in a N,N′ bidentate fashion and other two coordination sites are occupied by PPh₃. The ligand and the complexes are fluorescent and the fluorescence quantum yields of [Cu(L)(PPh₃)₂]ClO₄ and [Ag(L)(PPh₃)₂]NO₃ are higher than [Cu(L)₂]ClO₄ and [Ag(L)₂]NO₃. Cu(I) complexes show Cu(II)/Cu(I) quasireversible redox couple while Ag(I) complexes exhibit deposition of Ag(0) on the electrode surface during cyclic voltammetric experiments. gaussian 03 computations of representative complexes have been used to determine the composition and energy of molecular levels. An attempt has been made to explain solution spectra and redox properties of the complexes.     

Synthesis,spectroscopic characterization,crystal and molecular structure of [ReOX2(bopyH)(PPh3)] complexes: DFT calculations for [ReOCl2(bopyH)(PPh3)]

The reactions of [ReOX₃(PPh₃)₂] (X = Cl, Br) with benzoylpyridine (bopy) have been examined and novel [ReOX₂(bopyH)(PPh₃)] oxocompounds have been obtained. The complexes were structurally and spectroscopically characterised. In the both structures two-electron reduced form of benzoylpyridine is coordinated to the central ion. The electronic structure of [ReOCl₂(bopyH)(PPh₃)] has been calculated with the density functional theory (DFT) method, and additional information about binding has been obtained by NBO analysis. The UV–Vis spectrum of the [ReOCl₂(bopyH)(PPh₃)] has been discussed on the basis of TDDFT calculations.     

Synthesis,spectroscopic investigation,structural characterization,and DFT calculations of [ReX2(N2COPh)(CH3PhCN)(PPh3)2] (X=Cl,Br)

Reactions of [ReX₂(η ²-N₂COPh-N′,O)(PPh₃)₂] with 3-methylbenzonitrile give two iso-structural complexes, [ReX₂(N₂COPh)(CH₃PhCN)(PPh₃)₂] (X?=?Cl, Br). The crystal and molecular structures of [ReCl₂(N₂COPh)(CH₃PhCN)(PPh₃)₂] (1) and [ReBr₂(N₂COPh)(CH₃PhCN)(PPh₃)₂]?·?CH₂Cl₂ (2) were determined. The electronic structures were examined with density functional theory (DFT). The spin-allowed electronic transitions were calculated with the time-dependent DFT method, and the UV-Vis spectrum has been discussed.     

Novel oxorhenium complexes with 2-(2′-hydroxyphenyl)-2-benzothiazolinato ligand: X-ray studies,spectroscopic characterization and DFT calculations

The [ReOX₂(hbt)(EPh₃)] (X = Cl, Br; E = As, P) chelates have been prepared in the reactions of [ReOX₃(EPh₃)₂] complexes (X = Cl, Br; E = P, As) with 2-(2′-hydroxyphenyl)-2-benzothiazole (hbtH) in acetone. From the reactions of [ReOX₃(PPh₃)₂] with hbtH two kind of crystals [ReOX₂(hbt)(PPh₃)] · MeCN and [ReOX₂(hbt)(PPh₃)] with different arrangement of halide ions (cis and trans) were isolated, whereas the [ReOX₃(AsPh₃)₂] oxocompounds react with hbtH to give only cis-halide isomers. The complexes were structurally and spectroscopically characterised. The electronic structures of both [ReOBr₂(hbt)(PPh₃)] isomers have been calculated with the density functional theory (DFT) method. The TDDFT/PCM calculations have been employed to produce a hundred of singlet excited-states starting from the ground-state geometry optimized in the gas phase of cis- and trans-halide isomers of [ReOBr₂(hbt)(PPh₃)] and the UV–Vis spectra of these complexes have been discussed on this basis.     

Synthesis,Spectroscopy, and Structures of Mono‐ and Dinuclear Copper(I) Halide Complexes with 1,3‐Imidazolidine‐2‐thiones

Copper(I) halides with triphenyl phosphine and imidaozlidine‐2‐thiones (L ‐NMe, L ‐NEt, and L ‐NPh) in acetonitrile/methanol (or dichloromethane) yielded copper(I) mixed‐ligand complexes: mononuclear, namely, [CuCl(κ¹‐S‐L ‐NMe)(PPh₃)₂] ( 1 ), [CuBr(κ¹‐S‐L ‐NMe)(PPh₃)₂] ( 2 ), [CuBr(κ¹‐S‐L ‐NEt)(PPh₃)₂] ( 5 ), [CuI(κ¹‐S‐L ‐NEt)(PPh₃)₂] ( 6 ), [CuCl(κ¹‐S‐L ‐NPh)(PPh₃)₂] ( 7 ), and [CuBr(κ¹‐S‐L ‐NPh)(PPh₃)₂] ( 8 ), and dinuclear, [Cu₂(κ¹‐I)₂(μ‐S‐L ‐NMe)₂(PPh₃)₂] ( 3 ) and [Cu₂(μ‐Cl)₂(κ¹‐S‐L ‐NEt)₂(PPh₃)₂] ( 4 ). All complexes were characterized with analytical data, IR and NMR spectroscopy, and X‐ray crystallography. Complexes 2 – 4 , 7 , and 8 each formed crystals in the triclinic system with P$\bar{1}$ space group, whereas complexes 1 , 5 , and 6 crystallized in the monoclinic crystal system with space groups P2₁/c, C2/c, and P2₁/n, respectively. Complex 2 has shown two independent molecules, [(CuBr(κ¹‐S‐L ‐NMe)(PPh₃)₂] and [CuBr(PPh₃)₂] in the unit cell. For X = Cl, the thio‐ligand bonded to metal as terminal in complex 4 , whereas for X = I it is sulfur‐bridged in complex 3 .     

New oxorhenium complexes with 2-(2′-hydroxyphenyl)-2-benzoxazolinato ligand. X-ray structure and DFT calculations for [ReOX2(hbo)(AsPh3)] and [ReOX2(hbo)(PPh3)] complexes

The reactions of [ReOX₃(AsPh₃)₂] and [ReOX₃(PPh₃)₂] with 2-(2′-hydroxyphenyl)-2-benzoxazoline (Hhbo) have been examined and [ReOX₂(hbo)(AsPh₃)] and [ReOX₂(hbo)(PPh₃)] (X = Cl, Br) complexes have been obtained. The crystal and molecular structures of [ReOCl₂(hbo)(AsPh₃)] (1) and [ReOBr₂(hbo)(PPh₃)] (4) have been determined. The electronic structures of 1 and 4 have been calculated with the density functional theory (DFT) method. The spin-allowed electronic transitions of 1 and 4 have been calculated with the time-dependent DFT method, and the UV–Vis spectra of these complexes have been discussed.     

Molecular and spectroscopic properties of hydridecarbonyl ruthenium complexes with pyrazine carboxylic acid ligands

The hydride carbonyl ruthenium(II) [RuH(CO)(pyzCOO)(PPh₃)₂] (1), [RuH(CO)(pyz-2,3-COO[CH₃])(PPh₃)₂]·H₂O (2) and dinuclear Ru(II)/Ru(III) [RuH(CO)(PPh₃)(pyz-2,3-COO)Ru(CO)Cl₂(PPh₃)₂] (3) complexes were synthesized and characterized by IR, ¹H, ³¹P NMR, UV-Vis spectroscopy and X-ray crystallography. The experimental studies were complemented by quantum chemical calculations, which were used to identify the nature of the interactions between the ligands and the central ion, and the orbital composition in the frontier electronic structure. Based on a molecular orbital scheme, the calculated results allowed the interpretation of the UV-Vis spectra obtained at an experimental level. The luminescence property of the complex 2 was determined. The ac magnetic susceptibility measurements showed a residual magnetism evidenced by the small values of the molar susceptibility, not exceeding 0.5 emu/mol at 2 K, a lack of a Curie-Weiss region and weak magnetic interactions below 20 K.     

Proton Affinities of Cationic Carbone Adducts [AC(PPh3)2]+ (A=Halogen,Hydrogen, Methyl) and Unusual Electronic Structures of the Cations and Dications [AC(H)(PPh3)2]2+

This work reports the syntheses and the first crystal structures of the cationic carbone adducts [FC(PPh₃)₂]⁺ and [BrC(PPh₃)₂]⁺ and the protonated dication [FC(H)(PPh₃)₂]²⁺, which are derived from the carbone C(PPh₃)₂. Quantum chemical calculations and bonding analyses were carried out for the series of cations [AC(PPh₃)₂]⁺ and dications [AC(H)(PPh₃)₂]²⁺, where A=H, Me, F, Cl, Br, I. The bonding analysis suggests that the cations are best described as phosphane complexes L→(CA)⁺←L (L=PPh₃), which are related to the neutral borylene adducts L→(BA)←L (L=cyclic carbene; A=H, aryl) that were recently isolated. The carbone adducts [AC(PPh₃)₂]⁺ possess a π electron lone pair at carbon and they can easily be protonated to the dications [AC(H)(PPh₃)₂]²⁺. The calculations of the dications indicate that the molecules are best represented as complexes L→(CHA)²⁺←L (L=PPh₃) where a carbene dication is stabilized by the ligands. The central carbon atom in the cations and even in the dications carries a negative partial charge, which is larger than the negative charge at fluorine. There is also the peculiar situation in which the carbon–fluorine bonds in [FC(PPh₃)₂]⁺ and [FC(H)(PPh₃)₂]²⁺ exhibit the expected polarity with the negative end at fluorine, but the carbon atom has a larger negative charge than fluorine. Given the similarity of carbodiphosphorane C(PPh₃)₂ and carbodicarbene C(NHC)₂, we expect that analogous compounds [AC(NHC)₂]⁺ and [AC(H)(NHC)₂]²⁺ with similar features as [AC(PPh₃)₂]⁺ and [AC(H)(PPh₃)₂]²⁺ can be isolated.     

Ruthenium(II) carbonyl complexes with N-[di(alkyl/aryl)carbamothioyl]benzamide derivatives and triphenylphosphine as effective catalysts for oxidation of alcohols

Ruthenium(II) complexes, [RuCl(L)(CO)(PPh₃)₂] {where L?=?N-[di(alkyl/aryl)carbamothioyl]benzamide derivatives}, are prepared from reaction between [RuHCl(CO)(PPh₃)₃] and N-[di(alkyl/aryl)carbamothioyl]benzamide derivatives in toluene and characterized by elemental analysis and spectral data (electronic, infrared, ¹H NMR, and ³¹P NMR). The combination of [RuCl(L)(CO)(PPh₃)₂] (0.01?mmol) and N-methylmorpholine-N-oxide (NMO) (3?mmol) is an active catalyst for the oxidation of primary, secondary, cyclic, allylic, aliphatic, and benzylic alcohols to their corresponding aldehydes and ketones at room temperature. The oxidation protocol is simple to operate and gives the corresponding carbonyl compounds good to excellent yields.     

Solvent‐assisted formation of ruthenium(II)/copper(I) complexes containing thiourea derivatives: Synthesis,crystal structure,density functional theory,enzyme mimetics and in vitro biological perspectives

N ,N ‐[(diethylamino)(thiocarbonyl)]‐substituted benzamidine ligands have been synthesized from the reaction of N ,N ‐[(diethylamino)(thiocarbonyl)]benzimidoyl chloride with functionalized amines such as 2‐aminophenol and 2‐picolylamine. The reaction of N ,N ‐[(diethylamino)(thiocarbonyl)]‐2‐hydroxyphenylbenzamidine ( H ₂ L ₁ ) with ruthenium(II) precursor [RuHCl(CO)(PPh₃)₃] afforded complex 1 of the type [Ru(L₁)(CO)(PPh₃)₂] in which the ligand coordinated in tridentate ONS mode. The reaction of H ₂ L ₁ with copper precursor [Cu(CH₃COO)(PPh₃)₂] induced C═N bond cleavage of the ligand and afforded complex 3 of the type [Cu(1,1‐DT)(Cl)(PPh₃)₂] (1,1‐DT = 1,1‐diethylthiourea) in which the ligand coordinated in a monodentate fashion. The ligand N ,N ‐[(diethylamino)(thiocarbonyl)]‐2‐picolylbenzamidine ( HL ₂ ) reacted with ruthenium(II) and copper(I) precursors to form complex 2 of the type [Ru(1,1‐DT)(Cl₂)(CO)(PPh₃)₂] and complex 3 , respectively, in which the ligand underwent C═N cleavage and coordinated in a monodentate fashion via C═S group. In complexes 1 and 2 , the two triphenylphosphine co‐ligands coordinated in trans position whereas, in complex 3 , the two triphenylphosphine co‐ligands coordinated in cis position. All the compounds were characterized using infrared, UV–visible, (¹H, ¹³C, ³¹P) NMR, ESI‐MS and elemental analyses. The molecular structures of ligand H ₂ L ₁ and complexes 1 – 3 were determined using X‐ray crystallography, which confirmed the coordination mode of the ligands with metals. The crystal structure of complexes 1 and 2 revealed a distorted octahedral geometry around the ruthenium ion and the structure of complex 3 indicated a tetrahedral geometry around the copper ion. With the X‐ray structures, density functional theory computations were carried out to determine the electronic structure of the compounds. The interactions of complexes 1 – 3 with calf thymus DNA and bovine serum albumin protein were investigated using UV–visible and fluorescence spectroscopic and viscometric methods. Catecholase‐ and phosphatase‐like activities promoted by complexes 1 – 3 under physiological conditions have been studied. In vitro anticancer activities have been demonstrated by MTT assay, acridine orange/ethidium bromide and diamidino‐2‐phenylindole staining against various cancerous cell lines.     

Homo- und Hetero-Zweikernkomplexe des D2h-symmetrischen Bis(chelat)-Liganden 2,2′-Bipyrimidin mit den elektronenreichen Metallfragmenten Mo(CO)4, Re(CO)3Cl, [Cu(PPh3)2]+ und [Ru(bpy)2]2+

Homo- and Heterodinuclear Complexes of the D_2h-symmetric Bis(chelate) Ligand 2,2′-Bipyrimidine with Electron-Rich Metal Fragments Mo(CO)₄, Re(CO)₃Cl, [Cu(PPh₃)₂]⁺, and [Ru(bpy)₂]²⁺ All homo- and heterodinuclear complexes (L_nM)(μ-bpym)(ML_n)′, bpym = 2,2′-bipyrimidine, ML_n (ML_n)′ = Mo(CO)₄, Re(CO)₃Cl, [Cu(PPh₃)₂]⁺, [Ru(bpy)₂]²⁺, have been synthesized and studied by cyclic voltammetry, absorption spectroscopy, and by electron spin resonance of singly reduced forms. The individual capabilities of the low-valent metal fragments to undergo oxidation and to shift the reduction potential of the bpym π acceptor ligand on coordination combine to result in variable electrochemical potential differences. After consideration of different Franck-Condon factors, absorption intensities, additional low-lying unoccupied orbitals of the bridging acceptor ligand and solvatochromic effects, we have assigned the considerably varying metal-to-ligand charge transfer transitions in the visible.     

Pseudoelementverbindungen. XI. [1] Untersuchungen zum Komplexbildungsverhalten von Cyanamidonitrat [NO2NCN]−

Pseudoelement Compounds. XI. [1] Investigations on the Coordination Behaviour of Cyanamidonitrate [NO₂NCN]^? With the ionic, potentially ambidentate ligand cyanamidonitrate complexes of the types [MX(PPh₃)₃], [MX(PPh₃)₂]₂ (M?Cu^I, Ag^I) and trans-[Pt(H)X(PPh₃)₂] (X^??[NO₂NCN]^?) are introduced. The new compounds are characterized by ¹H NMR, ³¹P NMR, and IR spectroscopy. The crystal structures of [Cu(NO₂NCN)(PPh₃)₂]₂ and [Ag(NO₂NCN)(PPh₃)₂]₂ are reported. In the complexes [MX(PPh₃)₃] and trans-[Pt(H)X(PPh₃)₂] cyanamidonitrate is unidentately coordinated through the nitrile group end-on. In the dimeric complexes [MX(PPh₃)₂]₂ the anion acts bidentately as a bridging ligand. Surprisingly, both coordinative bonds are formed through nitrogen atoms of the NCN group.     

Synthesis,crystal, molecular and electronic structures of thiocyanate hydrido-carbonyl ruthenium(II) complexes with imidazole derivatives ligands

[RuH(CO)(SCN)(PPh₃)₃] and [RuH(CO){SCN}(PPh₃)₂(L)]{SCN} complexes (where L = benzimidazole, 2-(2-pyridyl)benzimidazole and 2,2′-bis(4,5-dimethylimidazolyl)) have been prepared and studied by IR, NMR, UV–Vis spectroscopy and X-ray crystallography. Electronic structures and bonding of the obtained complexes were defined on the basis of DFT method. Values of the ligand field parameter 10Dq and Racah’s parameters were estimated for the studied compounds, and the luminescence properties were determined.     

Ruthenium(III) complexes with N-(acetyl)-N′-(5-R-salicylidene)hydrazines: Syntheses,structures and properties

The reactions of 1 mol equiv. each of [Ru(PPh₃)₃Cl₂] and N-(acetyl)-N′-(5-R-salicylidene)hydrazines (H₂ahsR, R = H, OCH₃, Cl, Br and NO₂) in alcoholic media afford simultaneously two types of complexes having the general formulae [Ru(HahsR)(PPh₃)₂Cl₂] and [Ru(ahsR)(PPh₃)₂Cl]. The complexes have been characterized by elemental analysis, magnetic, spectroscopic and electrochemical measurements. Molecular structures of [Ru(HahsH)(PPh₃)₂Cl₂] and [Ru(ahsH)(PPh₃)₂Cl] have been confirmed by X-ray crystallography. In both species, the PPh₃ ligands are trans to each other. The bidentate HahsH⁻ coordinates to the metal ion via the O atom of the deprotonated amide and the imine–N atom in [Ru(HahsH)(PPh₃)₂Cl₂]. In HahsH⁻, the phenolic OH is involved in a strong intramolecular hydrogen bond with the uncoordinated amide N atom forming a seven-membered ring. In [Ru(ahsH)(PPh₃)₂Cl], the tridentate ahsH²⁻ binds to the metal ion via the deprotonated amide O, the imine N and the phenolate O atoms. In the electronic spectra, the green [Ru(HahsR)(PPh₃)₂Cl₂] and brown [Ru(ahsR)(PPh₃)₂Cl] complexes display several absorptions in the ranges 385–283 and 457–269 nm, respectively. Both complexes are low-spin and display rhombic EPR spectra in frozen solutions. Both types of complexes are redox active and display a quasi-reversible ruthenium(III) to ruthenium(II) reduction which is sensitive to the polar effect of the substituent on the chelating ligand. The reduction potentials are in the ranges −0.21 to −0.12 and −0.42 to −0.21 V (versus Ag/AgCl) for [Ru(HahsR)(PPh₃)₂Cl₂] and [Ru(ahsR)(PPh₃)₂Cl], respectively.     

Chemistry of a family of semiquinone monochelates of carbonyl ruthenium(II) generated by reacting quinones with hydridic species

The reactions of [Ru(H)(Cl)(CO)(PPh₃)₃] with 3,5-di-tert-butyl-o-benzoquinone (dbq) and 3,4,5,6-tetrachloro-o-benzoquinone (tcq) have afforded the corresponding semiquinone complexes [Ru^II(dbsq)(Cl)(CO)(PPh₃)₂] and [Ru^II(tcsq)(Cl)(CO)(PPh₃)₂], respectively. The reaction of [Ru(H)₂(CO)(PPh₃)₃] with tcq has furnished [Ru^II(tcsq)(H)(CO)(PPh₃)₂]. Structure determination of [Ru(dbsq)(Cl)(CO)(PPh₃)₂] has revealed that it is a model semiquinonoid chelate with two equal C---O lengths ( 1.291(6) and 1.296(6) Å). The complexes are one-electron paramagnetic (1.85μ_B) and their EPR spectra in fluid media display a triplet structure (g2.00) due to superhyperfine coupling with two trans-³¹P atoms (A_iso17 G). The stretching frequency of the CO ligand increases by 20 cm⁻¹ in going from [Ru(dbsq)(Cl)(CO)(PPh₃)₂] to [Ru(tcsq)(Cl)(CO)(PPh₃)₂] consistent with electron withdrawal by chloro substituents. For the same reason the E_1/2 values of the cyclic voltammetric quinone/semiquinone and semiquinone/catechol couples undergo a shift of 500 mV to higher potentials between [Ru(dbsq)(Cl)(CO)(PPh₃)₂] and [Ru(tcsq)(Cl)(CO)(PPh₃)₂].     

Coordination,oligomerisation and transfer hydrogenation of acetylenes by some ruthenium and osmium carboxylates: Crystal and molecular structures of bis(trifluoroacetato)carbonyl-(methanol) bis(triphenylphosphine)ruthenium(II) and (1,4-diphenylbut-1-en-3-yn-2-yl)trifluoroacetato-(carbonyl) bis(triphenylphosphine)ruthenium(II)

The hydrides [MH(O₂CCF₃)(CO)(PPh₃)₂] (M = Ru or Os) react with disubstituted acetylenes PhCCPh and PhCCMe to afford vinylic products [M{C(Ph)CHPh}(O₂CCF₃)(CO)(PPh₃)₂] and [M{C(Ph)CHMe}(O₂CCF₃)(CO) (PPh₃)₂]/[M{C(Me)CHPh}(O₂CCF₃)(CO)(PPh₃)₂] respectively. Acidolysis of these products with trifluoroacetic acid in cold ethanol liberates cis-stilbene and cis-PhHCCHMe respectively thus establishing the cis-stereochemistry of the vinylic ligands. The complexes [M(O₂CCF₃)₂(CO)(PPh₃)₂] formed during the acidolysis step undergo facile alcoholysis followed by β-elimination of aldehyde to regenerate the parent hydrides [MH(O₂CCF₃)(CO)(PPh₃)₂] and thereby complete a catalytic cycle for the transfer hydrogenation of acetylenes. The molecular structure of the methanol-adduct intermediate, [Ru(O₂CCF₃)₂(MeOH)(CO)(PPh₃)₂] has been determined by X-ray methods and shows that the coordinated methanol is involved in H-bonding with the monodentate trifluoroacetate ligand [MEO-H---OC(O)CF₃; O...O = 2.54 Å]. The hydrides [MH(O₂CCF₃)(CO) (PPh₃)₂]react with 1,4-diphenylbutadiyne to afford the complexes [M{C(CCPh)CHPh} (O₂CCF₃)(CO)(PPh₃)₂]. The ruthenium product, which has also been obtained by treatment of [RuH(O₂CCF₃)(CO)(PPh₃)₂] with phenylacetylene, has been shown by X-ray diffraction methods to contain a 1,4-diphenylbut-1-en-3-yn-2-yl ligand. The osmium complexes [Os(O₂CCF₃)₂(CO)(PPh₃)₂], [OsH(O₂CCF₃)(CO)(PPh₃)₂] and [Os{C(CCPh)CHPh}(O₂CCF₃)(CO)(PPh₃)₂] all serve as catalysts for the oligomerisation of phenylacetylene. Acetylene reacts with [Ru(O₂CCF₃)₂(CO)(PPh₃)₂] in ethanol to afford the vinyl complex [Ru(CHCH₂)(O₂CCF₃)(CO)(PPh₃)₂].     

Ni(II) complexes of unsymmetrical phenyl and phenethyl dithiocarbamates and triphenylphosphine

Unsymmetrical Ni(II) complexes of phenyl- and phenethyldithiocarbamate and PPh₃ of composition [NiX(HPhdtc)(PPh₃)], [NiX(HPhetdtc)(PPh₃)], [Ni(HPhdtc)(PPh₃)₂]ClO₄ and [Ni(HPhdtc)(PPh₃)₂]PF₆ {X?=?Cl, Br, I, NCS; HPhdtc?=?phenyldithiocarbamate, HPhetdtc?=phenethyldithiocarbamate, PPh₃?=?triphenylphosphine} have been synthesized. The complexes have been characterized by elemental and thermal analysis, IR and electronic spectroscopy, magnetochemical and conductivity measurements. Single-crystal X-ray analysis of [NiBr(HPhdtc)(PPh₃)]?·?CHCl₃ confirmed a distorted square planar coordination for the NiS₂PBr chromophore. For selected samples, the catalytic effects of graphite oxidation were studied.     

Molecular and spectroscopic properties of chloride and thiocyanate hydridecarbonyl ruthenium(II) complexes with pyridine derivative ligands

[RuH(CO)(dpa)(PPh₃)₂]X and [RuHX(CO)(pyCHPh)(PPh₃)₂] (X = Cl, NCS) complexes (where dpa = 2,2′-dipyridylamine, pyCHPh = 4-(3-phenylpropyl)pyridine) have been prepared and studied using IR, NMR, UV-Vis spectroscopies and X-ray crystallography. The electronic structures and bonding of the obtained complexes were defined on the basis of the DFT method. The electronic spectra of the complexes were calculated and associated with the structure of the molecular orbitals of the complexes. The luminescence properties of the complexes were determined.