New media in homogeneous catalysis: wet sodium or tetrabutylammonium hydrogensulfate salts for reppe syntheses catalyzed by a ru(ii) carbonyl complex

The ruthenium(II) complex fac-[Ru(CO)₂(H₂O)₃(C(O)C₂H₅)][CF₃SO₃] dissolved in aqueous tetrabutylammonium hydrogensulfate ([(CH₃(CH₂)₃)₄N][HSO₄]) or sodium hydrogensulfate (NaHSO₄) catalyzes the hydrocarboxylation of ethylene to propionic acid and additionally produces minor amounts of hydrocarbonylation products (diethyl ketone and propanal), under water-gas shift reaction conditions. This system is stable with a selectivity of 90% to propionic acid for high ethylene conversion. A turnover frequency of propionic acid, TOF(C₂H₅CO₂H)/24?h?=?5?×?10³ (TOF (C₂H₅CO₂H)?=?([(moles of C₂H₅CO₂H)/(moles of Ru)?×?rt)]?×?24?h) was achieved for Ru?=?7.45?×?10^?4?mol, [(CH₃(CH₂)₃)₄N][HSO₄]?=?80?g (2.36?×?10^?2?mol); H₂O?=?40?g (2.22?mol); CO?=?C₂H₄?=?20?g (total pressure?=?88?atm); T?=?150°C by a reaction time (rt) of 2.87?h. The countercation (sodium or tetrabutylammonium), the ruthenium concentration and the hydrogensulfate/H₂O ratio of the medium affect the catalytic reaction. A nonlinear dependence on total ruthenium concentration was shown. The data are discussed in terms of a potential catalytic cycle. Formation of propionic acid comes from hydrolysis, and formation of diethyl ketone and propanal comes from hydrogenolysis of the Ru-ketyl and Ru-acyl complexes, respectively.     

Heterobimetallische phosphanido-verbrückte Zweikern-Komplexe - Synthese von cis-rac-[(η-C5H4R)2Zr{μ-PH(2,4,6−iPr3C6H2)}2M(CO)4] (RMe,MCr,Mo; RH,MMo)

Heterobimetallic Phosphanido-bridged Dinuclear Complexes - Syntheses of cis-rac-[(η-C₅H₄R)₂Zr{μ-PH(2,4,6-ⁱPr₃C₆H₂)}₂M(CO)₄] (R?Me, M?Cr, Mo; R?H, M?Mo) The zirconocene bisphosphanido complexes [(η-C₅H₄R)₂Zr{PH(2,4,6-ⁱPr₃C₆H₂)}₂] (R?Me, H) react with [(NBD)M(CO)₄] (NBD?norbornadiene, M?Cr, Mo) to give only one diastereomer of the phosphanido-bridged heterobimetallic dinuclear complexes cis-rac-[(η-C₅H₄R)₂Zr{μ-PH(2,4,6-ⁱPr₃C₆H₂)}₂M(CO)₄] [R?Me, M?Cr ( 1 ), Mo ( 2 ); R?H, M?Mo ( 3 )]. However, no reaction was observed between [(η-C₅H₅)₂Zr{PH(2,4,6-^tBu₃ C₆H₂)}₂] and [Pt(PPh₃)₄]. 1—3 were characterised spectroscopically. For 1—3 , the presence of the racemic isomer was shown by NMR spectroscopy. No reaction was observed at room temperature for 3 and CS₂, (NO)BF₄, Me₃NO or PH(2,4,6-Me₃C₆H₂)₂. With Et₂AlH or PhC?CH decomposition of 3 was observed.     

N-heterocyclic carbene adducts of cyclopalladated ferrocenylchloropyrimidine: synthesis, structural characterization and application in the Sonogashira reaction

Three N-heterocyclic carbene (NHC) adducts of cyclopalladated ferrocenylchloropyrimidine, 2?C4 [PdCl{[(??⁵-C₅H₅)]Fe[(??⁵-C₅H₃)-N₂C₄H₂-Cl]}(NHCs)] have been prepared by reaction of the chloride-bridged palladacyclic dimer 1 [PdCl{[(??⁵-C₅H₅)]Fe[(??⁵-C₅H₃)-N₂C₄H₂-Cl]}]₂ with the corresponding imidazolium salts. These complexes were characterized by elemental analysis, IR, ESI?CMS and NMR. The use of these complexes as catalysts for the Sonogashira reaction was examined. Complex 4 proved to be an efficient catalyst for the Sonogashira reaction of aryl bromides and some activated aryl chlorides under copper- and amine-free conditions. Typically, using 0.1?C2?mol?% of catalyst in the presence of 1.5 equivalents of CsOAc as base in dimethylacetamide at 120?°C provided coupling products in good yields.     

Study of the reaction of MoOS2(S2CNR2)2 with PPh3 in 1,2-dichloroethane: Part I. Kinetics of the teaction of MoOS2(S2CNR2)2 with triphenylphosphine PPh3

The kinetics of the reaction of MoOS₂(S₂CNR₂)₂ (R = CH₃, C₂H₅, n-C₃H₇) with PPh₃ have been studied using a Stopped-flow method. It was found that these MoOS₂(S₂CNR₂)₂ complexes react with PPh₃ in the form of an irreversible second-order reaction. The rate constants at 25°C are respectively 48.4, 23.8, and 20.8 mol^?1 dm³ s^?1 and the activation energies are 4.8, 4.9, and 5.0 Kcal/mol with R = CH₃, C₂H₅, and n-C₃H₇.     

Zur Reaktivität von Disilylarsenido-Eisenkomplexen gegenüber Carbonsäurechloriden Die ersten Arsaalkenyl- und Diacylarsenidokomplexe. Röntgen-Strukturanalyse von Z-[(η5-C5H5)(CO)2Fe?AsC(OSiMe3)(t-Bu)]

On the Reactivity of Disilylarsenido Iron Complexes towards Carbonyl Chlorides: The First Arsaalkenyl- and Diacylarsenido Complexes. X-Ray Structure Analysis of Z-[(η⁵-C₅H₅)(CO)₂Fe? As?C(OSiMe₃)(t-Bu)] The reaction of equimolar amounts of (η⁵-C₅H₅)(CO)₂FeAs(SiMe₃)₂ ( 1a ) with the carbonyl chlorides RC(O)Cl (R = t-Bu, 2,4,6-Me₃C₆H₂ and 2,4,6-t-Bu₃C₆H₂) yields the arsaalkenyl complexes Z-[(η⁵-C₅H₅)(CO)₂Fe? As?;C(OSiMe₃)R ( 2–4 )]. The diacylarsenido complexes (η⁵-C₅H₅)(CO)₂Fe? As[C(O)R]₂ ( 5, 6 ) are generated by treatment of 1a with two equivalents of pivaloyl chloride or mesitoyl chloride, respectively. The As?C-double bond length of 2 (1.821(2) Å) was determined by single crystal x-ray analysis.     

π-cyclopentadienyls of nickel(II) : XV. Insertion reaction of RNCS into the nickel—carbon bond

η⁵-C₅H₅NiPBu₃CH(CN)₂ (I) readily undergoes ethyl- or phenyl-isothiocyanate insertion, producing the stable products η⁵-C₅H₅NiPBu₃SC(NRH) = C(CN)₂ (IIIa; R = C₂H₅, IIIb; R = C₆H₅. η⁵-C₅H₅NiPPh₃CH(CN)₂ (II) reacts with RNCS (R = C₂H₅ and C₆H₅) to undergo two types of insertion reaction; with C₂H₅NCS, η⁵C₅H₅NiPPh₃SC[N(C₂H₅)H] = C(CN)₂ (IVa) is obtained, with C₆H₅NCS, on the other hand, η⁵-C₅H₅NiPPh₃SC(NC₆H₅)CH(CN)₂ (IVb) is produced. p ]IIIa and IIIb react with PBu₃ to give ionic complexes [η⁵-C₅H₅Ni(PBu₃)₂]⁺ [SC(NC₂H₅H)C(CN)₂]^? (Va) and [η⁵-C₅H₅Ni(PBu₃)₂]⁺ [SC(NC₆H₅)CH(CN)₂]^?(Vb), respectively.     

Basicity of bisperhalophenyl aurates toward closed-shell metal ions: metallophilicity and additional interactions

The interaction of bisperhalophenyl aurates [AuR₂]^? (R?=?C₆F₅, C₆F₃Cl₂, and C₆Cl₅) with the closed-shell Ag⁺, Cu⁺, and Tl⁺ ions has been studied theoretically and compared with the experimentally known X-ray diffraction crystal structures. Initially, the aurates have been fully optimized at MP2 level of theory in a D _2h symmetry. The analysis of the basicity of the three aurates [AuR₂]^? (R?=?C₆F₅, C₆F₃Cl₂ and C₆Cl₅) against Ag⁺ ions in a C _2v symmetry has been calculated in point-by-point bsse-corrected interaction energy analysis at HF and MP2 levels of theory. Taking into account the experimental observation of additional interactions between the heterometals and C _ipso atoms at the perhalophenyl rings or halogen atoms at the ortho position of the perhalophenyl rings, dinuclear models of the type [AuR₂]^?···Ag⁺ (R?=?C₆Cl₅, and C₆F₅); [AuR₂]^?···Cu⁺ (R?=?C₆F₅, and C₆Cl₅) and [AuR₂]^?···Tl⁺ (R?=?C₆F₅, and C₆Cl₅) with a C _2v , C ₂ , and C _s symmetries have been optimized at DFT-B3LYP level. The interaction energies have been computed through bsse-corrected single point HF and MP2 calculations. The energy stabilization provided and the heterometal preference have been analyzed and compared with the experimental results.     

Syntheses,spectroscopic characterizations and crystal structures of diorganotin(IV)-oxo-carboxylates with 2-pyrazinecarboxylic acid or (2-pyrimidylthio)acetic acid

Eight diorganotin(IV)-oxo-carboxylates {[R₂Sn(O(O)CR′)]₂O}₂?·?Y (R′?=?C₄H₃N₂Y?= H₂OR?=?ⁿBu 1, Y?=?0 R?=?Me 2, Y?=?0 R?=?C₆H₅ 3, Y?=?0 R?=?C₆H₅CH₂ 4; R′?=?CH₂SC₄H₃N₂-2,6Y?=?0 R?=?ⁿBu 5, Y?=?CH₂Cl₂R?=?Me 6, Y?=?0 R?=?C₆H₅ 7, Y?=?0 R?= C₆H₅CH₂ 8) have been prepared in 1?:?1 molar ratios by reactions of diorganotin(IV) oxide with 2-pyrazinecarboxylic acid or (2-pyrimidylthio)acetic acid, respectively. All the complexes are characterized by elemental analysis, IR, ¹H NMR and ¹³C NMR spectra. Except for 2, 4 and 7, the complexes are also characterized by X-ray crystallography diffraction analyses, which reveal that the complexes adopt the familiar dicarboxylato tetraorganodistannoxane structural mode. Among them, the evident difference is that weak intramolecular interactions between Sn and N atoms are recognized in complexes 1 and 3. However, for complex 5 two different coordination modes are found in the same lattice.     

(Phosphine)gold(I) Complexes of Benzenedithioles. Crystal structures of 1,2-benzenedithiolato-bis[triphenyl-phosphinegold(I)] and bis(triethylphosphine)gold(I) bis(1,2-benzenedithiolato)gold(III)

The reaction of 1,2- and 1,3-benzenedithiol C₆H₄(SH)₂ with chloro(phosphine)gold(I) complexes R₃PAuCl (R = Et, Ph) in the presence of triethylamine in tetrahydrofuran gives stable gold(I) complexes 1,2-C₆H₄(SAuPR₃)₂ [R = Et ( 1 ) and Ph ( 2 )] or 1,3-C₆H₄(SAuPPh₃)₂ ( 3 ), respectively, in high yield. The compounds have been characterized by analytical and NMR spectroscopic data. From the reaction of 1,2-C₆H(SH)₂ with Et₃P? AuCl a by-product [(Et₃P)₂Au]⁺ [Au(1,2? C₆H₄S₂)₂]^? ( 4 ) has also been isolated in low yield. The crystal structures of compounds 2 and 4 have been determined by single crystal X-ray diffraction. The gold(I) atoms in complex 2 are two-coordinate with bond angles S? Au? P of 175.2(1) and 159.5(1)°, Au? S bond distances of 2.304(1) and 2.321(1) å, and a short Au…?Au contact of 3.145(1) Å. The gold(I) atom in the cation of complex 4 is also linearly two-coordinate with a P? Au? P angle of 170.1(1) Å and Au? P distances of 2.296(3) and 2.298(3) Å. The geometry of the anion in 4 shows a square-planar coordination of gold(III) by two chelating 1,2-benzenedithiolate ligands with Au? S distances between 2.299(3) and 2.312(3) Å (for two crystallographically independent, centrosymmetrical anions in the unit cell).     

Übergangsmetall-substituierte Acylphosphane und Phosphaalkene. 17 [1] Synthese und Struktur der μ-Isophosphaalkin-Komplexe [(η5-C5H5)2(CO)2Fe2(μ-CO)(μ-CPC6H2R3-2,4,6)] (R = Me,iPr, tBu)

Transition Metal Substituted Acylphosphanes and Phosphaalkenes. 17. Synthesis and Structure of the μ-Isophosphaalkyne Complexes [(η⁵-C₅H₅)₂(CO)₂Fe₂(μ-CO)(μ-C?PC₆H₂R₃)] (R = Me, iPr, tBu) . Condensation of (η⁵-C₅H₅)₂(CO)₂Fe₂(μ-CO)(μ-CSMe)}⁺SO₃CF₃^? ( 6 ) with 2,4,6-R₃C₆H₂PH(SiMe₃) ( 7 ) ( a : R = Me, b : R = iPr, c : R = tBu) affords the complexes (η⁵-C₅H₅)₂(CO)₂Fe₂(μ-CO)(η-C?PC₆H₂R₃-2,4,6) ( 9 a–c ) with edge-bridging isophosphaalkyne ligands as confirmed by the x-ray structure analysis of 9 a .     

Syntheses and Reactions of Dimolybdenum Alkyne Compounds Containing Functionally Substituted Ligands. The Crystal Structure of [Co2Mo2(μ4-CHCH)(μ-CO)4(CO)4-(η5-C5H4C(O)Me)2]

Abstract

Three dimolybdenum alkyne complexes containing functionally substituted ligands [Mo₂(μ-CHCH)(CO)₄(η⁵?C₅H₄C(O)R)₂] [R ? OEt, (1a); R ? Me, (1b); R ? Ph, (1c)] were synthesized by reactions of acetylene with in situ generated metal-metal triply bonded complexes [Mo(CO)₂(η⁵?C₅H₄C(O)R)]₂ (R ? OEt, Me, Ph). Further reaction of (1a), (1b) or (1c) with Co₂(CO)₈ in refluxing toluene gave another three new butterfly compounds [Co₂Mo₂-(μ₄-CHCH)(μ-CO)₄(CO)₄(η⁵-C₅H₄C(O)R)₂] [R ? OEt, (2a); R ? Me, (2b); R ? Ph, (2c)]. The resulting compounds were characterized by elemental analyses, IR, ¹H NMR and MS. The crystal structure of (2b) was determined by single-crystal X-ray analysis. The results indicate that the existence of functional groups on the cyclopentadienyl ring has an influence on the reactivity of this type of complex.     

Studies on synthesis,determination of CMC values,kinetics and the mechanism of iron(II) reduction of surfactant–Co(III)–ethylenediamine complexes in aqueous acid medium

The surfactant–Co(III) complexes of the type cis-[Co(en)₂AX]²⁺ (A?=?Tetradecylamine, X?=?Cl^?,?Br^?) were synthesised from corresponding dihalogeno complexes by the ligand substitution method. The critical micelle concentration (CMC) values of these surfactant complexes in aqueous solution were obtained from conductance measurements. The kinetics and mechanism of iron(II) reduction of surfactant–Co(III) complexes, cis-[Co(en)₂(C₁₄H₂₉NH₂)Cl](ClO₄)₂ and cis-[Co(en)₂(C₁₄H₂₉NH₂)Br] (ClO₄)₂ ions were studied spectrophotometrically in an aqueous acid medium by following the disappearance of Co(III) using an excess of the reductant under pseudo-first-order conditions: [Fe(II)]?=?0.25?mol?dm^?3, [H⁺]?=?0.1?mol?dm^?3, [μ]?=?1.0?mol?dm^?3 ionic strength in a nitrogen atmosphere at 303, 308 and 313?K. The reaction was found to be of second order and showed acid independence in the range [H⁺]?=?0.05–0.25?mol?dm^?3. The second-order rate constant increased with surfactant–Co(III) concentration and the presence of aggregation of the complex itself altered the reaction rate. The effects of [Fe(II)], [H⁺] and [μ] on the rate were determined. Activation and thermodynamic parameters were computed. It is suggested that the reaction of [Fe(II)] with Co(III) complex proceeds by an inner-sphere mechanism.     

Synthesis,spectral and antimicrobial studies of chlorodiorganotin(IV)[3(2′-hydroxyphenyl)-5-(4-substitutedphenyl) pyrazolinates]

Chlorodiorganotin(IV)pyrazolinates of the type R₂SnCl(C₁₅H₁₂N₂O?·?X) [where C₁₅H₁₂N₂O?·?X?=?3(2′-Hydroxyphenyl)-5(4-X-phenyl)pyrazoline {where X?=?H (a); CH₃ (b); OCH₃ (c); Cl (d) and R?=?Me, Pr ⁿ and Ph}] have been synthesized by reaction of R₂SnCl₂ with the sodium salt of pyrazolines in 1?:?1 molar ratio, in anhydrous benzene. These newly synthesized derivatives have been characterized by elemental analysis (C, H, N, Cl and Sn), molecular weight measurement and spectral studies [IR and multinuclear NMR (¹H, ¹³C and ¹¹⁹Sn)]. The bidentate behavior of the ligands was confirmed by IR, ¹H and ¹³C NMR spectral data. Trigonal bipyramidal structure around tin(IV) for R₂SnCl(C₁₅H₁₂N₂O?·?X) is suggested. The free pyrazoline and some chlorodiorganotin(IV) pyrazolinates have been screened for their antibacterial and antifungal activities. Some chlorodiorganotin(IV) pyrazolinates exhibit higher antibacterial and antifungal effect than free pyrazoline and some antibiotics.     

Organische Phosphorverbindungen XXXVIII. Darstellung und Eigenschaften von Tris-(dialkoxyphosphonyl-methyl)-, Tris-(alkoxyphosphinyl-methyl)-und Tris-(oxophosphoranyl-methyl)-phosphinsäureestern sowie der entsprechenden Säuren [1]

Tris-chloromethyl-phosphine oxide, (ClCH₂₎₃ P?O(I), is obtained by chlorination of (HOCH₂₎₃P?O with PCl₅ or (C₆H₅₎₃PCl₂, and also by oxidation of (CICH₂₎₃P?O and (ClCh₂₎₂(CH₃)P?O. High yields of tris-(dialkyloxyphosphonly-methyl)-phosphine oxides, [RO₂(O)PCH_2]2P?O (II) (R?CH₃, C₂H₅, iso-C₃H₇, n-C₄H₉, 2- ethyl-hexyl), tris (alkyloxyphosphinyl-methyl)-phosphine oxides, [R₂(O)PCH_2]3P?O(R = C₆H₅, CH₃) are obtained by heating tris-chloromethyl-phosphine oxides, [(RO) (R′) (O)PCH_2]3P?O (R = C₄H₉, R′? C₆H₅) and tris-(oxophosphoranyl-phosphine oxides with phosphites, phosphonites and phosphinites, respectively, at 170–180°C for several hours. Compounds II possess an extraordinarily high absorption capacity. Thus a warm. 2% solution of II (R = C₂H₅) in benzene solidifies completely on cooling so that no benzene can be poured off. Tris-dihydroxyphosphonyl-methyl)-phosphine oxide, [(HO)₂(O)PCH_2]3P?O, obtained by hydrolysis of II (R ? C₂H₅) with refluxing conc. HCl or by thermal decomposition of II (R ? iso-C₃H₇) at 190°, titrates in aqueous solution as a hexabasic acid with breaks at pH = 4,4 (three equivalents) and pH = 10,7 (three equivalents). It forms crystalline salts with amines, alkali and alkaline earth metals, and is an excellent chelating agent. The ¹H- and ^31?P-NMR. spectra of all the compounds prepared are discussed.     

Syntheses and structural characterization of organotin(IV) complexes derived from reaction of 2,3-diphenylpropionic acid and various alkyltin salts

Five new organotin(IV) complexes, [(R₃Sn)(O₂C₁₅H₁₃)] _n (R?=?Me: 1; nBu: 2), [RSn(O)(O₂C₁₅H₁₃)]₆ (R?=?Ph: 3), [(R₂Sn)₂(O₂C₁₅H₁₃)₂(μ ₃-O)]₂ (R?=?Me: 4), and [(R₂Sn)(O₂C₁₅H₁₃)₂] (R?=?nBu: 5), have been prepared by the reaction of 2,3-diphenylpropionic acid and the corresponding organotin chloride with sodium ethoxide in methanol. All the complexes were characterized by elemental analysis, FT-IR, NMR (¹H, ¹³C, ¹¹⁹Sn) spectroscopy, TGA, and X-ray crystallography. The structural analyses reveal that 1 and 2 are 1-D infinite polymeric chains with Sn in syn–anti conformation. Complex 3 has a drum structure with six Sn centers. Complex 4 has a supramolecular chain-like ladder through weak intermolecular Sn?···?O interactions. Complex 5 is a monomer, connected into a 1-D polymer through intermolecular C–H?···?O interactions. Complexes 1 and 5 crystallize in the orthorhombic space groups P212121 and P21212, which are chiral space groups.     

Synthesis,structure, and kinetic studies on [RuCl2(NCCH3)2(cod)]

[RuCl₂(NCCH₃)₂(cod)], an alternative starting material to [RuCl₂(cod)] _n for the preparation of ruthenium(II) complexes, has been prepared from the polymer compound and isolated in yields up to 87% using a new work-up procedure. The compound has been obtained as a yellow solid without water of crystallization. The complexes [RuCl₂(NCR)₂(cod)] spontaneously transform into dimers [Ru₂Cl(μ-Cl)₃(cod)₂(NCR)] (R?=?Me, Ph). ¹H NMR kinetic experiments for these transformations evidenced first-order behavior. [RuCl₂(NCPh)₂(cod)] dimerizes slower by a factor of ten than [RuCl₂(NCCH₃)₂(cod)]. The following activation parameters, ΔH ^#?=?114?±?3?kJ?mol^?1 and ΔS ^#?=?66?±?9?J?K^?1?mol^?1 for R?=?CH₃CN (ΔG ^#?=?94?±?5?kJ?mol^?1, 298.15?K) and ΔH ^#?=?122?±?2?kJ?mol^?1 and ΔS ^#?=?75?±?6?J?K^?1?mol^?1 for R?=?Ph (ΔG ^#?=?100?±?4?kJ?mol^?1, 298.15?K), have been calculated from the first-order rate constants in the temperature range 294–323?K. The kinetic parameters are in agreement with a two-step mechanism with dissociation of acetonitrile as the rate-determining step. The molecular structures of [Ru₂Cl(μ-Cl)₃(cod)₂(NCR)] (R?=?Me, Ph) have been determined by X-ray diffraction.     

The formation of dimetallocycles from reactions of alkynes with (η-C5Me5)2Rh2(CO)2; X-ray structure of [(η-C5Me5)2Rh2(η-CO) {μ-η2,η2-C(O)C2-(CF3)2}]

The complexes (η-C₅Me₅)₂Rh₂(μ-CO) {μ-η²,η²-C(O)CRCR} are obtained from reactions between (η-C₅Me₅)₂Rh₂(CO)₂ and the alkynes RCCR (R  CF₃, CO₂Me, or Ph) at 25°C. The molecular geometry of the complex with R  CF₃ has been established by X-ray diffraction; the bridging 'ene-one' unit adopts a μ-η²,η² conformation. Other complexes isolated from these reactions include (η-C₅Me₅)Rh(C₆R₆) (R  CF₃, CO₂Me), (η-C₅Me)₂Rh₂(C₄R₄) (R  CO₂Me) and (η-C₅Me₅)₂Rh₂(CO₂C₂R₂) (R  Ph). The reaction between (η-C₅Me₅)₂Rh₂(CO)₂ and C₆F₅CCC₆F₅ gives (η-C₅Me₅)₂Rh₂(CO)₂(C₆F₅C₂C₆F₅). Mononuclear complexes such as (η-C₅Me₅)Co(C₄R₄CO) are the major products isolated from reactions between (η-C₅Me₅)₂CO₂(CO)₂ and alkynes at 25°C.     

Organometallic formate complexes of platinum(II)

The compounds trans-[Pt(OCHO)R(PPh₃)₂] (R = C₆Cl₅; 2,3,4,6-C₆HCl₄; 2,3,4,5-C₆HCl₄; 2,5-C₆H₃Cl₂) have been prepared by treatment of [PtIR(PPh₃)₂] with AgClO₄ followed by reaction with NaOCHO in methanol. The cis isomers have been obtained by the direct reaction of HCO₂H with compounds containing PtHg bonds. For these and the analogous compounds containing C₆F₅ ligands, the dependence of J(³¹P¹⁹⁵Pt) on R has been studied, and the effects of cis-R shown to be in the opposite direction from those of trans-R ligands.     

Darstellung und Charakterisierung von kationischen η2-1-Buten- und Acetonitrilkomplexen

Preparation and Characterization of Cationic η²-1-Butene and Acetonitrile Complexes The reaction of the species η⁵-C₅H₅M(CO)_n-σ-C₄H₇ (M = Fe, Mo, W; n = 2, 3) with (C₆H₅)₃CBF₄ yielded – instead of the expected cationic butadiene complexes of the type [η⁵-CpM(CO)_n?1-η⁴-C₄H₆][BF₄], which would have been formed in case of hydride cleavage – compounds of the type [η⁵-CpM(CO)_n η²-C₄H₈][BF₄], which were formed by protonation of the σ-C₄H₇ ligands. The reaction proceeded quantitatively. The BF₄^? anion can be substituted by other anions, such as ClO₄^?, B(C₆H₅)₄^?, PF₄^?, and [Cr(SCN)₄(NH₃)₂]^? in the complexes obtained. The mechanism of the reaction leading to the η²-bonded 1-butene complexes was determined by isotope experiments. In trying to recrystallize the butene complexes from acetonitrile the cationic complexes [η⁵-C₅H₅ Fe(CO)₂CH₃CN]BF₄ and [η⁵-C₅H₅ M(CO)₃CH₃CN]BF₄ were observed; the X-ray structure analysis of the former is reported.     

Coordination complexes of titanium,zirconium and tin having metal-carbon bonds with dibasic NSO donor Schiff base ligand. Syntheses and characterization

The reaction of 3-formylsalicylic acid with morpholine N-thiohydrazide produces 3-carboxy-2-hydroxybenzaldehyde morpholine N-thiohydrazone (H₂chbmth) which remains in equilibrium in solution with its corresponding thiol form H₃chbmthol having an NSO donor set of atoms. The reactions of the thiohydrazone ligand with different organometallic compounds viz. R₂MCl₂ (R?=?π-C₅H₅ & M?=?Ti/Zr; R?=?Me/Ph & M?=?Sn; R?=?OMe & M?=?Sn), (π-C₅H₅)₂Ti(OMe)Cl₂ and RMCl3 (R?=?Me/Ph & M?=?Sn; R?=?π-C₅H₅ & M?=?Ti) leading to the syntheses of many new organometallic derivatives have been studied. In all of the complexes the dianion of the H₃chbmthol ligand functions as a dibasic tridentate NSO donor. The reactions of [(π-C₅H₅)Ti(Hchbmthol)Cl] and [MeSn(Hchbmthol)Cl], isolated in this study, with Me₃SiE (where, E stands for NMe₂ and C≡CPh) and MeSH have also been studied and many new organoderivatives of these two metal ions isolated. All the compounds under study have been characterized by elemental analyses, magnetic susceptibilities, molar conductance values, molecular weights and spectroscopic (UV-Vis, IR, ¹H NMR) data. Based upon these data the geometry of the compounds has also been proposed.