The tris(triphenylphosphine)osmium zerovalent complexes Os(CO)2(PPh3)3, .Os(CO)(CNR)(PPh3)3, Os(CO)(CS)(PPh3)3, Os(CS)(cNR)(PPh3)3 and derived compounds

Detailed procedures for the syntheses of Os(CO)₂(PPh₃)₃, Os(CO)(CNR)-(PPh₃)₃ (R = p-tolyl), Os(CO)(CS)(PPh₃)₃ and Os(CS)(CNR)(PPh₃)₃, together with the derived complexes Os(CO)₂(CS)(PPh₃)₂, Os(CO)(CS)(CNR)(PPh₃)₂, Os(η²-C₂H₄)(CO)(CNR)(PPh₃)₂, Os(η²-C₂H₄)(CO)(CS)(PPh₃)₂, Os(η²CS₂)(CO)₂-(PPh₃)₂, Os(η²CS₂)(CO)(CS)(PPh₃)₂, Os(η²-CS₂)(CO)(CNR)(PPh₃)₂, Os(η²PhC₂Ph)(CO)₂(PPh₃)₂ and OsH(C2Ph)(CO)₂(PPh₃)₂ are described.     

Syntheses and crystal structures of linear coordinated complexes of Ag with the ligands C(PPh3)2 and (HC{PPh3}2)

The cationic complexes [({Ph₃P}₂C)Ag(C{PPh₃}₂)]X (2⁺, X = Cl, BF₄) with a linear arrangement of the ligands were obtained from the reaction of C(PPh₃)₂ (1) with the appropriate AgX in THF. The ³¹P NMR spectrum of the cation 2⁺ exhibits a doublet with J(Ag,P) = 15.3 Hz. The cation was also formed when the adduct O₂C ← 1 was allowed to react with AgX in CH₂Cl₂ in the first step as shown by ³¹P NMR; however, deprotonation of the solvent finally produced the cation (HC{PPh₃}₂)⁺, (H1)⁺ quantitatively. In the absence of coordinating anions, the tricationic complex [({Ph₃P}₂CH)Ag(CH{PPh₃}₂)](BF₄)₃ (3), containing the cation (H1)⁺ as ligand, could be isolated by reacting AgBF₄ with the salt (H1)(BF₄). All compounds were characterized by IR and ³¹P NMR spectroscopy; the structures of the compounds [2]Cl·1.25THF, 3·5CH₂Cl₂, 3·4C₂H₄Cl₂, and (H1)(BF₄) could be established by X-ray analyses.     

Thiocarbonyl complexes of ruthenium(II). Synthesis of RuCl2(CS)(H2O)(PPh3)2 and RuHCl(CS)(PPh3)3

A high-yield synthesis of trans-RuCl₂(CS)(H₂O)(PPh₃)₂ from RuCl₂(PPh₃)₃ and CS₂ is described. The coordinated water molecule is labile, and introduction of CNR (R  p-toyl or p-chlorophenyl) leads to yellow trans-RuCl₂(CS)(CNR)(PPh₃)₂, which isomerises thermally to colourless cis-RuCl₂(CS)(CNR)(PPh₃)₂. Reaction of AgClO₄ with cis-RuCl₂(CS)(CNR)(PPh₃)₂ gives [RuCl(CS)(CNR)(H₂O)(PPh₃)₂]⁺, from which [RuCl(CS)(CO)(CNR)(PPh₃)₂]⁺ and [RuCl(CS)(CNR)₂(PPh₃)₂]⁺ are derived. Reaction of trans-RuCl₂(CS)(H₂O)(PPh₃)₂ with sodium formate gives Ru(η²-O₂CH)Cl(CS)(PPh₃)₂, which undergoes decarboxylation in the presence of (PPh₃) to give RuHCl(CS)(PPh₃)₃. Ru(η²-O₂CH)H(CS)(PPh₃)₂ and Ru(η²-O₂CMe)-H(CS)(PPh₃)₂ are also described.     

Synthesis, characterization and antimicrobial studies of mixed ligand silver(I) complexes of triphenylphosphine and heterocyclic thiones: Crystal structure of bis[{(μ-diazinane-2-thione)(diazinane-2-thione)(triphenylphosphine)silver(I) nitrate}]

Mixed ligand silver(I) complexes of triphenylphosphine and heterocyclic thiones (imidazolidine-2-thione (Imt), diazinane-2-thione (Diaz) and 2-mercaptopyridine (Mpy)) having the general formulae [(Ph₃P)Ag(thione)₂]NO₃ and [(Ph₃P)₂Ag(thione)]NO₃ were prepared and characterized by elemental analysis, IR and NMR (¹H, ¹³C and ³¹P) spectroscopic methods. The crystal structure of one of the complexes, [Ag(Ph₃P)(Diaz)₂]₂(NO₃)₂ (1) was determined by X-ray crystallography. The title complex (1) is dinuclear, having each silver atom coordinated to three thione sulfur atoms of Diaz and to one phosphorus atom of PPh₃ in a nearly tetrahedral environment, with an average P-Ag-S bond angle of 108.5°. The spectral data of the complexes are consistent with sulfur coordination of the thiones to silver(I). Antimicrobial activities of the complexes were evaluated by minimum inhibitory concentrations and the results showed that the complexes exhibit a wide range of activity against two gram-negative bacteria (E. coli, P. aeruginosa) and molds (A. niger, P. citrinum), while the activities were poor against yeasts (C. albicans, S. cerevisiae).     

The reaction of trihydrobistriphenylphosphine iridium IrH3(PPh3)2 with diazonium salts

The reaction of IrH₃(PPh₃)₂ with p-substituted aryldiazonium salts gives the compounds [IrH₂(NHNC₆H₄R)(PPh₃)₂]⁺BF₄^- at low temperature (-10°C) and the o-metalated complexes [I$\text{rH(NHN}$C₆H₃R)(PPh₃)₂]⁺BF₄^- (R  F, OCH₃) at 40–50°C. The reactions of the o-metalated complexes with CO, PPh₃, NaI and HCl have been studied.     

Trifluoroacetylacetonate rhodium(III) methyl complexes, cis-[Rh(TFA)(PPh3)2(CH3)(L)][BPh4] and cis-[Rh(TFA)(PPh3)2(CH3)(I)] (L = CH3CN, NH3, pyridine), in comparison with their acetylacetonate analogs

The oxidative addition of CH₃I to planar rhodium(I) complex [Rh(TFA)(PPh₃)₂] in acetonitrile (TFA is trifluoroacetylacetonate) leads to the formation of cationic, cis-[Rh(TFA)(PPh₃)₂(CH₃)(CH₃CN)][BPh₄] (1), or neutral, cis-[Rh(TFA)(PPh₃)₂(CH₃)(I)] (4), rhodium(III) methyl complexes depending on the reaction conditions. 1 reacts readily with NH₃ and pyridine to form cationic complexes, cis-[Rh(TFA)(PPh₃)₂(CH₃)(NH₃)][BPh₄] (2) and cis-[Rh(TFA)(PPh₃)₂(CH₃)(Py)][BPh₄] (3), respectively. Acetylacetonate methyl complex of rhodium(III), cis-[Rh(Acac)(PPh₃)₂(CH₃)(I)] (5), was obtained by the action of NaI on cis-[Rh(Acac)(PPh₃)₂(CH₃)(CH₃CN)][BPh₄] in acetone at −15 °C. Complexes 1-5 were characterized by elemental analysis, ³¹P{¹H}, ¹H and ¹⁹F NMR. For complexes 2, 3, 4 conductivity data in acetone solutions are reported. The crystal structures of 2 and 3 were determined. NMR parameters of 1-5 and related complexes are discussed from the viewpoint of their isomerism.     

Tuning the sulfur-heterometal interaction in organolead(IV) complexes of [Pt2(μ-S)2(PPh3)4]

Reactions of [Pt₂(μ-S)₂(PPh₃)₄] with Ph₃PbCl, Ph₂PbI₂, Ph₂PbBr₂ and Me₃PbOAc result in the formation of bright yellow to orange solutions containing the cations [Pt₂(μ-S)₂(PPh₃)₄PbR₃]⁺ (R₃ = Ph₃, Ph₂I, Ph₂Br, Me₃) isolated as PF₆⁻ or BPh₄⁻ salts. In the case of the Me₃Pb and Et₃Pb systems, a prolonged reaction time results in formation of the alkylated species [Pt₂(μ-S)(μ-SR)(PPh₃)₄]⁺ (R = Me, Et). X-ray structure determinations on [Pt₂(μ-S)₂(PPh₃)₄PbMe₃]PF₆ and [Pt₂(μ-S)₂(PPh₃)₄PbPh₂I]PF₆ have been carried out, revealing different coordination modes. In the Me₃Pb complex, the (four-coordinate) lead atom binds to a single sulfur atom, while in the Ph₂PbI adduct coordination of both sulfurs results in a five-coordinate lead centre. These differences are related to the electron density on the lead centre, and indicate that the interaction of the heterometal centre with the {Pt₂S₂} metalloligand core can be tuned by variation of the heteroatom substituents. The species [Pt₂(μ-S)₂(PPh₃)₄PbR₃]⁺ display differing fragmentation pathways in their ESI mass spectra, following initial loss of PPh₃ in all cases; for R = Ph, loss of PbPh₂ occurs, yielding [Pt₂(μ-S)₂(PPh₃)₃Ph]⁺, while for R = Me, reductive elimination of ethane gives [Pt₂(μ-S)₂(PPh₃)₃PbMe]⁺, which is followed by loss of CH₄.     

Synthesis and characterisation of HRuRh3(CO)12. Crystal structures of HRuRh3(CO)12, HRuRh3(CO)10(PPh3)2 and HRuCo3(CO)10(PPh3)2

A new ruthenium-rhodium mixed-metal cluster HRuRh₃(CO)₁₂ and its derivatives HRuRh₃(CO)₁₀(PPh₃)₂ and HRuCo₃(CO)₁₀(PPh₃)₂ have been synthesized and characterized. The following crystal and molecular structures are reported: HRuRh₃(CO)₁₂: monoclinic, space group P2₁/c, a 9.230(4), b 11.790(5), c 17.124(9) Å, β 91.29(4)°, Z = 4; HRuRh₃(CO)₁₀(PPh₃)₂·C₆H₁₄: triclinic, space group P$\text{1}$, a 11.777(2), b 14.079(2), c 17.010(2) Å, α 86.99(1), β 76.91(1), γ 72.49(1)°, Z = 2; HRuCo₃(CO)₁₀(PPh₃)₂·CH₂Cl₂: triclinic, space group P$\text{1}$, a 11.577(7), b 13.729(7), c 16.777(10) Å, α 81.39(4), β 77.84(5), γ 65.56°, Z = 2. The reaction between Rh(CO)₄^? and (Ru(CO)₃Cl₂)₂ tetrahydrofuran followed by acid treatment yields HRuRh₃(CO)₁₂ in high yield. Its structural analysis was complicated by a 80–20% packing disorder. More detailed structural data were obtained from the fully ordered structure of HRuRh₃(CO)₁₀(PPh₃)₂, which is closely related to HRuCo₃(CO)₁₀(PPh₃)₂ and HFeCo₃(CO)₁₀(PPh₃)₂. The phosphines are axially coordinated.     

Molybdenum and tungsten complexes with the heteroallyl-like Ph2P(O)C(S)NR− (R  Me,Ph) as ligand. X-ray structural analysis of Mo(CO)2(PPh3)(Ph2P(O)C(S)NPh)2 · CH2Cl2; A 4 : 3 piano-stool configuration

Ph₂P(O)C(S)N(H)R (R  Me, Ph) reacts with M(CO)₃(η⁵-C₅H₅)Cl (M  Mo, W) in the presence of Et₃N to give M(CO)₂(η⁵-C₅H₅)(Ph₂P(O)C(S)NR). The deprotonated ligand coordinates in a bidentate manner through N and S to give a four-membered ring system. M(CO)₃(PPh₃)₂Cl₂ (M  Mo, W) reacts with Ph₂P(O)C(S)N(H)R (R  Me, Ph) in the presence of Et₃N to give complexes in which the central metal atoms are seven coordinate through two ligands bonded via O and S to form five-membered ring systems, one PPh₃, and two CO groups. The complexes were characterised by elemental analyses, IR, ¹H NMR, and ³¹P NMR spectroscopy, and an X-ray structural analysis of Mo(CO)₂(PPh₃)(Ph₂P(O)C(S)NPh)₂ · CH₂Cl₂.     

Formation and structural characterization of novel polynuclear palladium selenolato complexes [Pd3Se(SePh)3(PPh3)3]Cl and [Pd6Cl2Se4(SePh)2(PPh3)6]

In addition to well-known dinuclear phenylselenolato palladium complexes, the reaction of [PdCl₂(PPh₃)₂] and NaSePh affords small amounts of novel trinuclear and hexanuclear complexes [Pd₃Se(SePh)₃(PPh₃)₃]Cl (1) and [Pd₆Cl₂Se₄(SePh)₂(PPh₃)₆] (2). Complex 1 is triclinic, P1?, a=13.6310(2), b=16.2596(2), c=16.9899(3) Å, α=83.1738(5), β=78.9882(5), γ=78.7635(5)°. Complex 2 is monoclinic, C2/c, a=25.7165(9), b=17.6426(8), c=27.9151(14) Å, β=110.513(2)°. There are no structural forerunners for 1, but the hexanuclear complex 2 is isostructural with [Pd₆Cl₂Te₄(TeR)₂(PPh₃)₆] (R=Ph, C₄H₃S) that have been observed as one of the products in the oxidative addition of R₂Te₂ to [Pd(PPh₃)₄]. Mononuclear palladium complexes may play a significant role as building blocks in the formation of the polynuclear complexes.     

Fulvene—platinum complexes: x-ray crystal structure of [Pt(η2-C5H4CPh2)(PPh3)2]

Bis(cycloocta-1,5-diene)platinum reacts with 2,3,4,5-tetraphenylfulvene to afford the complex [Pt(η²-CH₂C₅Ph₄)(cod)] (cod  C₈H₁₂) in which the metal atom is coordinated to the exo-cyclic double bond of the fulvene. Related compounds [Pt(η²-CH₂C₅Ph₄L₂] (L  PPh₃, PMePh₂, PMe₂Ph, AsPh₃ or CNBu^t have also been prepared and characterised. Reaction of the complexes [Pt(C₂H₄)₂(L)] (L  P(cyclo-C₆H₁₁)₃, PPh₃ or AsPh₃) with 2,3,4,5-tetraphenylfulvene yields the compounds [Pt(C₂H₄)(η²-CH₂C₅PH₄)(L)]. NMR data for the new species are reported and discussed. 6,6-Diphenylfulvene reacts with [Pt(cod)₂] and PPh₃ ($\text{1}\text{2}$ mol ratio) to give the complex [Pt(η²-C₅H₄CPh₂)-(PPh₃)₂] in which the metal atom is bonded to carbon atoms C(2) and C(3) of the fulvene ring. This was established by an X-ray diffraction study. Crystals are monoclinic, space group P2₁/n, with Z  4 in a unit cell of dimensions a  13.761(4), b  21.653(13), c  17.395(6) Å, β,  104.46(2)°. The structure has been solved and refined to R  0.064 (R′  0.064) for 3139 independent diffracted intensifies measured at room temperature. The platinum atom is in a trigonal environment formed by the two ligated phosphorus atoms and the CC bond of the fulvene which is elongated to 1.52(3) Å. The c₅ fulvene ring is planar, and makes an angle of 108° with the coordination plane around the platinum. In this plane the metal atom is slightly asymmetrically bonded with PtC 2.15(2) and 2.24(2) Å, and PtP 2.280(6) and 2.301(6) Å.     

Synthesis of [Ru(CO)2(PPh3)(SP)] and [Ru(CO)(PPh3)2(SP)] and their catalytic activities for the hydroamination of phenylacetylene

The reaction of [Ru(CO)₂(PPh₃)₃] (1) with o-styryldiphenylphophine (SP) (2) gave [Ru(CO)₂(PPh₃)(SP)] (3) in 83% yield. This styrylphosphine ruthenium complex 3 can also be synthesized by the reaction of [Ru(p-MeOC₆H₄NN)(CO)₂(PPh₃)₂]BF₄ (4) with NaBH₄ and 2 in 50% yield. When “Ru(CO)(PPh₃)₃” generated by the reaction of [RuH₂(CO)(PPh₃)₃] (8) with trimethylvinylsilane reacted with 2, [Ru(CO)(PPh₃)₂(SP)] (10) was produced in moderate yield as an air sensitive solid. The spectral and X-ray data of these complexes revealed that the coordination geometries around the ruthenium center of both complexes corresponded to a distorted trigonal bipyramid with the olefin occupying the equatorial position and the C-C bonding in the olefin moiety in 3 and 10 contained a significant contribution from a ruthenacyclopropane limiting structure. Complexes 3 and 10 showed catalytic activity for the hydroamination of phenylacetylene 11 with aniline 12. Ruthenium complex 3 in the co-presence of NH₄PF₆ or H₃PW₁₂O₄₀ proves to be a superior catalyst system for this hydroamination reaction. In the case of the reaction using H₃PW₁₂O₄₀ as an additive, ketimines (13) was obtained in 99% yield at a ruthenium-catalyst loading of 0.1 mol%. Some aniline derivatives such as 4-methoxy, 4-trifluoromethyl-, and 4-bromoanilines can also be used in this hydroamination reaction.     

Synthese,Schwingungsspektren und Kristallstrukturen der Nitratoargentate (Ph4P)[Ag(NO3)2(CH3CN)]·CH3CN und (Ph4P)[Ag2(NO3)3]

Synthesis, Vibrational Spectra, and Crystal Structures of the Nitrato Argentates (Ph₄P)[Ag(NO₃)₂(CH₃CN)]·CH₃CN and (Ph₄P)[Ag₂(NO₃)₃] Tetraphenylphosphonium bromide reacts in acetonitril suspension with excess silver nitrate to give (Ph₄P)[Ag(NO₃)₂(CH₃CN)]·CH₃CN ( 1 ), whereas (Ph₄P)[Ag₂(NO₃)₃] ( 2 ) is obtained in a long‐time reaction from (Ph₄P)Br and excess AgNO₃ in dichloromethane suspension. Both complexes were characterized by vibrational spectroscopy (IR, Raman) and by single crystal structure determinations. 1 : Space group P2₁/c, Z = 4, lattice dimensions at 193 K: a = 1781.5(3), b = 724.8(1), c = 2224.2(3) pm, β = 96.83(1)°, R₁ = 0.0348. 1 contains isolated complex units [Ag(NO₃)₂(CH₃CN)]^?, in which the silver atom is coordinated by the chelating nitrate groups and by the nitrogen atom of the solvated CH₃CN molecule with a short Ag—N distance of 220.7(4) pm. 2 : Space group I2, Z = 4, lattice dimensions at 193 K: a = 1753.4(4), b = 701.7(1), c = 2105.5(4) pm, R₁ = 0.072. In the polymeric anions [Ag₂(NO₃)₃]^? each silver atom is coordinated in a chelating manner by one nitrate group and by two oxygen atoms of two bridging nitrate ions. In addition, each silver atom forms a weak π‐bonding contact with a phenyl group of the (Ph₄P)⁺ ions with shortest Ag···C separations of 266 and 299 pm, respectively, indicating a (4+1) coordination of silver atoms.     

Chelate structures of 5-(H/Br)-2-hydroxybenzaldehyde-4-allyl-thiosemicarbazones (H2L): Synthesis and structural characterizations of [Ni(L)(PPh3)] and [Ru(HL)2(PPh3)2]

The reactions of 5-R-2-hydroxybenzaldehyde-4-allyl-thiosemicarbazone {R: H (L¹); Br (L²)} with [M^II(PPh₃)nCl₂] (M = Ni, n = 2 and M = Ru, n = 3) in a 1:1 molar ratio have given stable solid complexes corresponding to the general formula [Ni(L)(PPh₃)] and [Ru(HL)₂(PPh₃)₂]. While the 1:1 nickel complexes are formed from an ONS donor set of the thiosemicarbazone and the P atom of triphenylphosphine in a square planar structure, the 1:2 ruthenium complexes consist of a couple from each of N, S and P donor atoms in a distorted octahedral geometry. These mixed-ligand complexes have been characterized by elemental analysis, IR, UV–Vis, APCI-MS, ¹H and ³¹P NMR spectroscopies. The structures of [Ni(L²)(PPh₃)] (II) and [Ru(L¹H)₂(PPh₃)₂] (III) were determined by single crystal X-ray diffraction.     

Cleavage of the sulfur-sulfur bond in 2,4-dinitrophenyl 4-substituted phenyl disulfides by trans-[IrX(CO)(PPh3)2]

A series of 2,4-dinitrophenyl 4-Y-phenyl disulfides (Y=NO₂, Br, F, H, CH₃, or CH₃O) have been shown to react with trans-IrX(CO)(PPh₃)₂ (X=Cl, Br, or I) in refluxing benzene to form “oxidative-elimination” products of the type, [IrX(SC₆h₄Y)(SC₆H₃(NO₂)₂)(CO)(PPh₃)]₂. The physical properties of these complexes are discussed in relation to their structure in the solid state and in solution. In particular, available infrared spectral data indicate that these complexes contain 2,4-dinitrobenzenethiolato bridging groups and that the substituted arenethiolato ligand is trans to carbon monoxide.     

A novel imido-transfer reaction of aldehydes with Ph3PNTs using RuCl2(PPh3)3 as catalyst

(N-Tosylimino)triphenylphosphorane (Ph₃PNTs) was found to be an efficient imido-transfer reagent for the imidation of a variety of aldehydes using RuCl₂(PPh₃)₃ as the catalyst.     

Intra- and intermolecular hydrogen bonds in [Ag(PPh3)3(HL)] complexes [H2L: H2xspa = 3(aryl)-2-sulfanylpropenoic acids; H2cpa = 2-cyclopentylidene-2-sulfanylacetic acid]

Compounds of the type [Ag(PPh₃)₃(HL)] {H₂xspa=3(aryl)-2-sulfanylpropenoic acids: x = Clp [3-(2-chlorophenyl)-], -o-mp [3-(2-methoxyphenyl)-], -p-mp [3-(4-methoxyphenyl)-], -o-hp [3-(2-hydroxyphenyl)-], -p-hp [3-(4-hydroxyphenyl-); H₂cpa = 2-cyclopentylidene-2-sulfanylacetic acid} were synthesized and characterised by IR and NMR (¹H ¹³C and ³¹P) spectroscopy and by FAB mass spectrometry. The crystal structures of [Ag(PPh₃)₃(HClpspa)], [Ag(PPh₃)₃(H-o-mpspa)], [Ag(PPh₃)₃(H-p-mpspa)] and [Ag(PPh₃)₃(Hcpa)] reveal the presence of discrete molecular units containing an intramolecular O-H···S hydrogen bond between the S atom and one of the O atoms of the COOH group. This intramolecular hydrogen bond remains in [Ag(PPh₃)₃(H-o-hpspa)]·EtOH and [Ag(PPh₃)₃(H-p-hpspa)] but in both cases polymeric structures are built on the basis of O-H···O interactions that involve the -OH substituent of the phenyl group of the sulfanylpropenoate fragment.     

Complexes of N-thiophosphorylthiourea (EtO)2P(O)CH2C6H4-4-[NHC(S)NHP(S)(OiPr)2] with Zn(II), Cd(II), Co(II) and Cu(PPh3)(I)

Reaction of O,O’-diisopropylthiophosphoric acid isothiocyanate (iPrO)₂P(S)NCS with diethyl 4-aminobenzylphosphonate (EtO)₂P(O)CH₂C₆H₄-4-NH₂ leads to the new N-thiophosphorylated thiourea (EtO)₂P(O)CH₂C₆H₄-4-[NHC(S)NHP(S)(OiPr)₂] (HL). Reaction of the potassium salt of HL with Zn(II), Cd(II) and Co(II) in aqueous EtOH leads to complexes of formula M(L-S,S’)₂ (ML₂). Heteroligand copper(I) complex of HL and triphenylphosphine was prepared by the reaction of the potassium salt KL and Cu(PPh₃)₃I. Copper in complex Cu(PPh₃)L is bound by one PPh₃ and one SCNPS fragment of the chelating ligand. Compounds obtained were investigated by IR, UV–Vis, ¹H and ³¹P{¹H} NMR spectroscopy, and microanalysis. The structures of HL and Cu(PPh₃)L were investigated by single crystal X-ray diffraction analysis.     

Novel bimetallic Ru-Pt and Fe-Pt Complexes [M(C5R5)(L)2(μ,η1:η2-P4{Pt(PPh3)2})]Y: Synthesis, structure, and exchange processes

Novel bimetallic Ru-Pt and Fe-Pt complexes, [M(C₅R₅)(L)₂(η¹-P₄)]Y (M = Ru, Fe; R = H, Me; L = PPh₃, 1/2Dppf (Ph₂P(C₅H₄)Fe(C₅H₄)PPh₂), 1/2Dppe (Ph₂PCH₂CH₂PPh₂); Y = PF₆, CF₃SO₃, BPh₄) were synthesized for the first time by the reaction of η¹-tetraphosphorus complexes of ruthenium(II) and iron(II), [M(C₅R₅)(L)₂(η¹-P₄)]Y with platinum(0) complex [Pt(η²-C₂H₄)(PPh₃)₂] in acetone. The structures and compositions of the title complexes were studied by the ³¹P NMR, correlated ³¹P-³¹P NMR COSY, NOESY, ¹H-spectroscopy, and elemental analysis. The carbene-like fragment Pt(PPh₃)₂ generated in situ was found to be inserted at the P-P bond of the η¹-coordinated tetraphosphorus and migrate between the phosphorus atoms of the obtained ligand μ, η¹: η²-P₄. The exchange process in the novel complexes was investigated. Original Russian Text ? D.N. Akbayeva, 2007, published in Koordinatsionnaya Khimiya, 2007, Vol. 33, No. 9, pp. 673–680.     

Synthesis and characterization of methylpalladium(II) dithiolate complexes of the type [PdMe(SS)(ER3)] (SS = S2CNR 2, S2COEt, S2P(OR)2, S2 PPh2; ER3 = PMePh2, PPh3, AsPh3)

Methylpalladium(II) dithiolate complexes of the type [PdMe(SS)(ER₃] (SS = S₂ CNR₂ (R = Me or Et), S₂COEt, S₂P(OR)₂ (R = Et, ⁿPr, ⁱPr), S₂PPh₂; ER₃ = PMePh₂, PPh₃, AsPh₃) have been synthesized by the reaction of [Pd₂Me₂(μ-Cl)₂(PMePh₂)₂] with sodium/potassium/ammonium salts of the dithio acid or by treatment of [PdMeCl(cod)] with ER₃ followed by sodium/potassium/ammonium salts of the dithio ligand. All the complexes were characterized by elemental analysis, IR and nuclear magnetic resonance (¹H, ³¹P) data.