Synthesis and DFT calculations of oxido and phenylimido-rhenium(V) complexes incorporating the N,O donor ligand 2-[(2-hydroxyethylimino)methyl]phenol

The reactions of equimolar amounts of trans-[ReOC1₃(PPh₃)₂] or trans-[Re(NPh)(PPh₃)₂Cl₃] with a Schiff base formed by condensation of 2-hydroxy-4-methoxybenzaldehyde and ethanolamine (H₂L) result in the formation of cis-[ReO(HL)PPh₃Cl₂] (1a) and trans-[Re(NPh)(HL)(PPh₃)Cl₂] (2b), respectively, in good yields. 1a and 2b have been characterized by a range of spectroscopic and analytical techniques. The X-ray crystal structures of 1a and 2b reveal that 1a is an octahedral cis-Cl,Cl oxorhenium(V) complex, while 2b is a trans-Cl,Cl phenylimidorhenium(V) complex. The complexes are weakly emissive at room temperature with quantum yields of 10^?4. Density functional theory calculations of the electronic properties of the complexes were performed and are in agreement with the experimental results. The complexes display quasi-reversible Re(V)/Re(VI) redox couples in acetonitrile. There is reasonable agreement between the experimental and calculated redox potentials of 1a and 2b.     

Platinum(II) Mono-N1-(2"-Tetrahydrofuranyl)-5-Fluorouracilate Complexes with Ammonia

The reaction between cis-[Pt(NH₃)₂Cl₂], N¹-(2"-tetrahydrofuranyl)-5-fluorouracil (HL), and NaOH (taken in a molar ratio of 1 : 1 : 1) or between cis-[Pt(NH₃)₂Cl₂], HL, and Ag₂O (taken in the molar ratio of 1 : 1 : 0.5) was used to synthesize complexes Ia (in the case of NaOH) or Ib (in the case of Ag₂O) with composition Pt(NH₃)₂LCl. The model complex [Pt(NH₃)₃L]NO₃ (II) was synthesized by the reaction between [Pt(NH₃)₃Cl]Cl, HL, AgNO₃, and Ag₂O (1 : 1 : 1 : 0.5). The obtained compounds were characterized by chemical analysis, chromatography, thermogravimetry, conductometry, potentiometry, IR, electronic, and NMR spectroscopies. Complexes Ia and Ib were found to have both similar and different properties. The structures of the compounds and the type of L^– coordination to platinum(II) were suggested. Cytotoxic properties of Iaand Ib were studied.     

The synthesis of a cationic ylide complex of platinum(II) by the reaction of tetrakis(triphenylphosphine)platinum(O) with choloroiodomethane.

The reaction of Pt(PPh₃)₄ with CH₂Cl1 in benzene yields the cationic ylide complex $\text{cis}$-[Pt(PPh₃)₂(CH₂PPh₃)Cl]I in high yield. This complex has been converted to $\text{cis}$-[(PPh₃)₂(CH₂PPh₃)X]X (X  Br or I) by reaction with LiBr or NaI. Reaction of $\text{cis}$-[Pt(PPH₃)I]I with iodine yields $\text{cis}$-[Pt(PPh₃)₂(CH₂PPh₃)I]I₃. Nmr data are given in support of the suggested structures.     

Nucleophilic Aromatic Addition Reactions of the Metallabenzenes and Metallapyridinium: Attacking Aromatic Metallacycles with Bis(diphenylphosphino)methane to Form Metallacyclohexadienes and Cyclic η2‐Allene‐Coordinated Complexes

The reactions of phosphonium‐substituted metallabenzenes and metallapyridinium with bis(diphenylphosphino)methane (DPPM) were investigated. Treatment of [Os{CHC(PPh₃)CHC(PPh₃)CH}Cl₂(PPh₃)₂]Cl with DPPM produced osmabenzenes [Os{CHC(PPh₃)CHC(PPh₃)CH}Cl₂{(PPh₂)CH₂(PPh₂)}]Cl ( 2 ), [Os{CHC(PPh₃)CHC(PPh₃)CH}Cl{(PPh₂)CH₂(PPh₂)}₂]Cl₂ ( 3 ), and cyclic osmium η²‐allene complex [Os{CH?C(PPh₃)CH?(η²‐C?CH)}Cl₂{(PPh₂)CH₂(PPh₂)}₂]Cl ( 4 ). When the analogue complex of osmabenzene 1 , ruthenabenzene [Ru{CHC(PPh₃)CHC(PPh₃)CH}Cl₂(PPh₃)₂]Cl, was used, the reaction produced ruthenacyclohexadiene [Ru{CH?C(PPh₃)CH?C(PPh₃)CH}Cl{(PPh₂)CH₂(PPh₂)}₂]Cl₂ ( 6 ), which could be viewed as a Jackson–Meisenheimer complex. Complex 6 is unstable in solution and can easily be convert to the cyclic ruthenium η²‐allene complexes [Ru{CH?C(PPh₃)CH?(η²‐C?CH)}Cl{(PPh₂)CH₂(PPh₂)}₂]Cl₂ ( 7 ) and [Ru{CH?C(PPh₃)CH?(η²‐C?CH)}Cl₂{(PPh₂)CH₂(PPh₂)}₂]Cl ( 8 ). The key intermediates of the reactions have been isolated and fully characterized, further supporting the proposed mechanism for the reactions. Similar reactions also occurred in phosphonium‐substituted metallapyridinium [OsCl₂{NHC(CH₃)C(Ph)C(PPh₃)CH}(PPh₃)₂]BF₄ to give the cyclic osmium η²‐allene‐imine complex [OsCl₂{NH?C(CH₃)C(Ph)?(η²‐C?CH)}{(PPh₂)CH₂(PPh₂)}(PPh₃)]BF₄ ( 11 ).     

Synthesis of chloro-carbonyl derivatives of rhenium,ruthenium, rhodium,iridium and platinum via reaction of the metal atoms with oxalyl chloride

Co-condensation of atoms of Re, Ru, Rh, Ir and Pt with oxalyl chloride gives metal chloro-carbonyl derivatives which may be used as precursors to the compounds [Re(CO)₄Cl]₂, [Ru(PMe₃)₃(CO)Cl₂], α-[Ru(CO)₃Cl(μ-Cl)]₂, [Ru(PPh₃)₂(CO)₂Cl₂], [Rh(CO)₂(μ-Cl)]₂, [Rh(PPh₃)₂COCl], [Ir(PPh₃)(CO)₂Cl₃] and cis-Pt(CO)₂Cl₂. Molybdenum atoms with oxalyl chloride give molybdenum-chloro derivatives.     

Synthesis and characterization of transition metal complexes of a new bidentate ligand {2-(diphenylphosphino)ethyl}benzylamine

A new bidentate ligand {2-(diphenylphosphino)ethyl}benzylamine(DPEBA) was synthesized and characterized based on the IR, mass and ¹H, ¹³C and ³¹P NMR spectra. Various complexes of platinum group metal ions and Ni(II) and Co(II) ions with the ligand were synthesized. Reaction of RuCl₂(PPh₃)₃ or RuCl₂(Me₂SO)₄ with the ligand DPEBA, resulted in formation of a penta-coordinate, Ru(II) species of the composition [RuCl(DPEBA)₂]Cl. Carbonylation of [RuCl(DPEBA)₂]Cl gave an octahedral carbonyl complex of the type [RuCl(CO)(DPEBA)₂]Cl. The reaction of RuCl₃·3H₂O or RuCl₃(AsPh₃)₂MeOH with a twofold excess of the ligand gave an octahedral Ru(III) cationic species [Ru(DPEBA)₂Cl₂]Cl. Carbonylation of the Ru(III) complex gave rise to a carbonyl complex [RuCl(CO)(DPEBA)₂]Cl₂. The ligand DPEBA reacts with cobalt(II) chloride in methanol to give the 1 : 1 complex [Co(DPEBA)Cl₂]. A series of Rh(I) complexes [Rh(DPEBA)₂Cl], [ RhCl(CO)(DPEBA)] and [Rh(DPEBA)₂]Cl were synthesized by the reaction of DPEBA with RhCl(PPh₃)₃, RhCl(CO)(PPh₃)₂ and [Rh(COD)Cl]₂, respectively. Reaction of [Ir(COD)Cl]₂ and IrCl(CO)(PPh₃)₂ with the ligand DPEBA, gave the square-planar complexes [Ir(DPBA)₂]Cl and [Ir(DPEBA)(CO)Cl], respectively. Octahedral cationic complexes of the type [M(DPEBA)₂Cl₂]Cl (M = Rh(III), Ir(III)) were synthesized by the reaction of the ligand DPEBA and rhodium and iridium trichlorides. Reaction of NiCl₂·6H₂O with DPEBA in 1 : 2 molar equivalents, in boiling butanol gave an octahedral neutral complex [Ni(DPEBA)₂Cl₂] which readily rearranges to the square-planar complex [Ni(DPEBA)₂]Cl₂ in methanol. Reaction of Pd(II) and Pt(II) chlorides with DPEBA gave square-planar, cationic complexes of the type [M(DPEBA)₂Cl]Cl (M = Pd, Pt). All the complexes were characterized on the basis of their analytical and spectral data.     

Reactivity of olefin an acetylene complexes of platinum(0) towards tetrachloro-o-benzoquinone

Tetracloro-o-benzoquinone reacts with (diphenylacetylene)bis(tirphenylphosphine)platinum(0) to give the novel platinum(II) diphenylacetylene complex, Pt(C₆Cl₄O₂)PhCCPh)(PPh₃), (I), which reacts with hydrogen halides to give the compelexes cis-PtX₂(PhCCPh((PPh₃), (X = Cl or Br). Hydrogen chloride also readily removes the tetrachloro-o-benzoquinoneligand from the adducts Ni(C₆Cl₄O₂)(Ph₂PCH₂CH₂PPh₂) and M(C₆Cl₄O₂)(PPh₃)₂, (M = Pd or Pt) but it has no reaction upon Ir(Cl)(C₆Cl₄O₂)(CO)(PPh₃)₂ at room temperature. The acetylene in (1) is susceptible to nucleophilic attact and reaction with diethylamine gives the vinyl adduct Pt(C₆Cl₄O₂)(CPhCPh)NHEt₂)(PPh₃). Other reactions of (I) have also been studied. Attemps to prepare other olefin or acetylene complexes of platinum(II) by the action of tetrachlor-o-benzoquinone on the complexes Pt(L)(PPh₃)₂, (L = PhCCH,(Et)(Me)(HO)CCCC(OH)(Me)(Et), HOCH₂OH, CF₃CCCF₃, CF₂CF₂, CF₂CH₂ or trans-PhCHCHPh) are also described.     

Synthesis of Pd(II) complexes containing the protonated form or molecule of 2-(3,5-dimethylpyrazol-1-yl)-4-methylquinoline (L). The crystal structure of [Pd(HL)Cl<Subscript>3</Subscript>]

The diamagnetic complexes [Pd(HL)Cl₃](I) and PdLCl₂(II), where L is 2-(3,5-dimethylpyrazol-1-yl)-4-methylquinoline, were obtained. According to X-ray diffraction data, the crystal structure of complex I consists of mononuclear acentric molecules. The coordination polygon PdNCl₃ is a distorted square (trapezium) made up of the pyrazole N atom of the monodentate ligand (cation HL⁺) and three Cl atoms. Complex II seems to contain the square polygon PdN₂Cl₂.     

Zweikernige Palladium(II)‐, Platin(II)‐ und Iridium(III)‐Komplexe von Bis[imidazol‐4‐yl]alkanen

Dinuclear Palladium(II), Platinum(II), and Iridium(III) Complexes of Bis[imidazol‐4‐yl]alkanes The reaction of bis(1,1′‐triphenylmethyl‐imidazol‐4‐yl) alkanes ((CH₂)_n bridged imidazoles L(CH₂)_nL, n = 3–6) with chloro bridged complexes [R₃P(Cl)M(μ‐Cl)M(Cl)PR₃] (M = Pd, Pt; R = Et, Pr, Bu) affords the dinuclear compounds [Cl₂(R₃P)M–L(CH₂)_nL–M(PR₃)Cl₂] 1 – 17 . The structures of [Cl₂(Et₃P)Pd–L(CH₂)₃L–Pd(PEt₃)Cl₂] ( 1 ), [Cl₂(Bu₃P)Pd–L(CH₂)₄L–Pd(PBu₃)Cl₂] ( 10 ), [Cl₂(Et₃P)Pd–L(CH₂)₅L–Pd(PEt₃)Cl₂] ( 3 ), [Cl₂(Et₃P)Pt–L(CH₂)₃L–Pt(PEt₃)Cl₂] ( 13 ) with trans Cl–M–Cl groups were determined by X‐ray diffraction. Similarly the complexes [Cl₂(Cp*)Ir–L(CH₂)_nL–Ir(Cp*)Cl₂] (n = 4–6) are obtained from [Cp*(Cl)Ir(μ‐Cl)₂Ir(Cl)Cp*] and the methylene bridged bis(imidazoles).     

Sulfur‐Assisted Intermolecular Triphenylphosphine Dissociation of Thiocarbamoyl Ligand in Platinum(II). X‐ray Structure of Complex [Pt(PPh3)2(η1‐SCNMe2)(Cl)]

Treatment of Pt(PPh₃)₄ with N,N‐dimethylthiocarbamoyl chloride, Me₂NC(=S)Cl, in dichloromethane at ?20 °C processes the oxidative addition reaction to produce platinum complex [Pt(PPh₃)₂(η¹‐SCNMe₂)(Cl)], 2 with releasing two triphenylphosphine molecules. The ³¹P{¹H} NMR spectra of complex 2 shows the dissociation of the triphenylphosphine ligand to form diplatinum complex [Pt(PPh₃)Cl]₂(μ,η²‐SCNMe₂)₂, 3 in which the two SCNMe₂ ligands coordinated through carbon to one metal center and bridging the other metal through sulfur. Complex 2 is characterized by X‐ray diffraction analysis.     

The platinum—carbon bond strength in Pt(PPh3)2(Cl)(CPhCHPh)

The enthalpies of the reactions 1 and 2 have been determined as ΔH = Pt(PPh₃)₂(CPhCPh)_cryst. + HCl_g → Pt(PPh₃)₂(Cl)(CPhCHPh)_cryst. (1) Pt(PPh₃)₂(CPhCPh)_cryst. + 2HCl_g → cis-Pt(PPh₃)₂Cl_2cryst. + trans-CHPhCHPh_g (2) ?90.2 ± 6 and ΔH = ?139.0 ± 16 kJ mol^?1, respectively; dissociation energies of bonds involving platinum are expressed by the relationship: 41 kJ mol^?1 + D(Pt-tolane) = 2D(PtCPhCHPh) = {D₁(PtCl) + D₂(PtCl)} ?350 kJ mol^?1     

Platinum,iridium and rhodium complexes with substituted bis-(diphenylphosphino)methane ligands Ph2PCH(R)PPh2 (R = Me,Ph or SiMe3)

Substituted phosphines of the type Ph₂PCH(R)PPh₂ and their Pt^II complexes [PtX₂{Ph₂PCH(R)PPh₂}] (R = Me, Ph or SiMe₃; X = halide) were prepared. Treatment of [PtCl₂(NCBu^t)₂] with Ph₂PCH(SiMe₃)-PPh₂ gave [PtCl₂(Ph₂PCH₂PPh₂)], while treatment with Ph₂PCH(Ph)PPh₂ gave [Pt{Ph₂PCH(Ph)PPh₂}₂]Cl₂. Reaction of p-MeC₆H₄C≡CLi or PhC≡CLi with [PtX₂{Ph₂PCH(Me)PPh₂}] gave [Pt(C≡CC₆H₄Me-p)₂-{Ph₂PCH(Me)PPh₂}] (X = I) and [Pt{Ph₂PC(Me)PPh₂}₂](X = Cl),while reaction of p-MeC₆H₄C≡CLi with [Pt{Ph₂PCH(Ph)PPh₂}₂]Cl₂ gave [Pt{Ph₂PC(Ph)PPh₂}₂]. The platinum complexes [PtMe₂(dpmMe)] or [Pt(CH₂)₄(dpmMe)] fail to undergo ring-opening on treatment with one equivalent of dpmMe [dpmMe = Ph₂PCH(Me)PPh₂]. Treatment of [Ir(CO)Cl(PPh₃)₂] with two equivalents of dpmMe gave [Ir(CO)(dpmMe)₂]Cl. The PF₆ salt was also prepared. Treatment of [Ir(CO)(dpmMe)₂]Cl with [Cu(C≡CPh)₂], [AgCl(PPh₃)] or [AuCl(PPh₃)] failed to give heterobimetallic complexes. Attempts to prepare the dinuclear rhodium complex [Rh₂(CO)₃(μ-Cl)(dpmMe)₂]BPh₄ using a procedure similar to that employed for an analogous dpm (dpm = Ph₂PCH₂PPh₂) complex were unsuccessful. Instead, the mononuclear complex [Rh(CO)(dpmMe)₂]BPh₄ was obtained. The corresponding chloride and PF₆ salts were also prepared. Attempts to prepare [Rh(CO)(dpmMe)₂]Cl in CHCl₃ gave [RhHCl(dpmMe)₂]Cl. Recrystallization of [Rh(CO)(dpmMe)₂]BPh₄ from CHCl₃/EtOH gave [RhO₂(dpmMe)₂]BPh₄. Treatment of [Rh(CO)₂Cl₂]₂ with one equivalent of dpmMe per Rh atom gave two compounds, [Rh(CO)(dpmMe)₂]Cl and a dinuclear complex that undergoes exchange at room temperature between two formulae: [Rh₂(CO)₂(μ-Cl)(μ-CO)(dpmMe)₂]Cl and [Rh₂(CO)₂-(μ-Cl)(dpmMe)₂]Cl. This revised version was published online in June 2006 with corrections to the Cover Date.     

Zur Reaktivität von alkylthioverbrückten 44‐CVE‐triangularen Platinclustern: Umsetzungen mit bidentaten Phosphanliganden

On the Reactivity of Alkylthio Bridged 44 CVE Triangular Platinum Clusters: Reactions with Bidentate Phosphine Ligands The 44 cve (cluster valence electrons) triangular platinum clusters [{Pt(PR₃)}₃(μ‐SMe)₃]Cl (PR₃ = PPh₃, 2a ; P(4‐FC₆H₄)₃, 2b ; P(n‐Bu)₃, 2c ) were found to react with PPh₂CH₂PPh₂ (dppm) in a degradation reaction yielding dinuclear platinum(I) complexes [{Pt(PR₃)}₂(μ‐SMe)(μ‐dppm)]Cl (PR₃ = PPh₃, 3a ; P(4‐FC₆H₄)₃, 3b ; P(n‐Bu)₃; 3e ) and the platinum(II) complex [Pt(SMe)₂(dppm)] ( 4 ), whereas the addition of PPh₂CH₂CH₂PPh₂ (dppe) to cluster 2a afforded a mixture of degradation products, among others the complexes [Pt(dppe)₂] and [Pt(dppe)₂]Cl₂. On the other hand, the treatment of cluster 2a with PPh₂CH₂CH₂CH₂PPh₂ (dppp) ended up in the formation of the cationic complex [{Pt(dppp)}₂(μ‐SMe)₂]Cl₂ ( 5 ). Furthermore, the terminal PPh₃ ligands in complex 3a proved to be subject to substitution by the stronger donating monodentate phosphine ligands PMePh₂ and PMe₂Ph yielding the analogous complexes [{Pt(PR₃)}₂(μ‐SMe)(μ‐dppm)]Cl (PR₃ = PMePh₂, 3c ; PMe₂Ph, 3d ). NMR investigations on complexes 3 showed an inverse correlation of Tolmans electronic parameter ν with the coupling constants ¹J(Pt,P) and ¹J(Pt,Pt). All compounds were fully characterized by means of NMR and IR spectroscopy. X‐ray diffraction analyses were performed for the complexes [{Pt{P(4‐FC₆H₄)₃}}₂(μ‐SMe)(μ‐dppm)]Cl ( 3b ), [Pt(SMe)₂(dppm)] ( 4 ), and [{Pt(dppp)}₂(μ‐SMe)₂]Cl₂ ( 5 ).     

Metal-thiophen derivatives. Organometallic compounds of palladium and platinum

Thienylmercury(II)chloride reacts with [Pd(PPh₃)₂Cl₂], [Pd(PPh₃)₄] and [Pt(PPh₃)₄] to afford new compounds containing a metal-2-thienyl linkage. The compound [Pd(PPh₃)₂(2-C₄H₃S)Cl] probably has trans stereochemistry.2-Bromothiophen undergoes oxidative addition with [Pd(PPh₃)₄] and [Pt(PPh₃)₄], probably via a radical mechanism. With [Pd(CO)(PPh₃)₃], a carbonyl inserted product is obtained. The bromo-metal(II) complexes have trans stereochemistry. The course of the reaction between 3-methyl-2-bromothiophen and Pd(PPh₃)₄ is more complex. Thus, there is evidence of some cis bromopalladium(II) compounds amongst the products, also there is good evidence to support the view that some isomerisation of 3-methyl-2-thienyl to 4-methyl-2-thienyl occurs during the reaction, thus giving greater molar quantities of [Pd(PPh₃)₂(4-CH₃-2-C₄H₂S)Br] than can be accounted for from any initial 4-methyl-2-bromothiophen impurity.The metallation of the thiophen ring, probably in the 4-position, with palladium(II) is described for 3-theylidene-4-methylaniline.     

New mono- and binuclear Pd(II) complexes containing 1,2,4-triazole moieties

The reaction of AMTT (AMTT = 4-amino-3-methyl-1,2,4-triazol-5-thione, HL1) with palladium(II) chloride and triphenylphosphane as a co-ligand in acetonitrile afforded the mononuclear Pd^II-complex [(PPh₃)Pd(HL1)Cl]Cl·2CH₃CN (1). The complex [(PPh₃)Pd(HL1)I]Cl·1/2H₂O (2) was prepared via halogen exchange between 1 and sodium iodide in methanol/acetonitrile. The first binuclear palladium(II) complex containing singly deprotonated HL1, [(PPh₃)₂ClPd(L1)Pd(PPh₃)Cl]Cl·1/3H₂O·CH₃OH (3), was prepared by the reaction of HL1 with palladium(II) chloride and triphenylphosphane in the presence of sodium acetate in methanol.     

THE REACTIONS OF [MoCl(GeCl3)(CO)3(NCMe)2] WITH NEUTRAL BI- AND TERDENTATE DONOR LIGANDS

Abstract

The reaction of [MoCl(GeCl₃)(CO)₃(NCMe)₂] with an equimolar quantity of L?L {L?L = 2,2′-bipy, 1,10-phen, Ph₂P(CH₂)_nPPh₂ (n = 1 or 2)} in CH₂Cl₂ at room temperature gave either [MoCl(GeCl₃)(CO)₃(L?L)] (L?L = 2,2′-bipy or 1,10-phen) (1 and 2) or [MoCl(GeCl₃)(CO)₂ (NCMe)(L?L)]{L?L = Ph₂P(CH₂)_nPPh₂ (n = 1 or 2) (3 or 4), respectively. Equimolar quantities of [MoCl(GeCl₃)(CO)₂(NCMe){Ph₂P(CH₂)PPh₂}] (3) and L?L {L?L = 2,2′-bipy or Ph₂P(CH)₂PPh₂} react in CH₂Cl₂ at room temperature to afford the cationic complexes [Mo(GeCl₃)(CO)₂{Ph₂P(CH₂) PPh₂}(L?L)]Cl (5 and 6) in good yield. The cationic nature of 6 was established by chloride exchange by reacting Na[BPh₄] with 6 in acetonitrile to give the tetraphenylborate complex [Mo(GeCl₃)(CO)₂{Ph₂P(CH₂)PPh₂}₂][BPh₄] (7). Reaction of equimolar quantities of [MoCl(GeCl₃) (CO)₃(NCMe)₂] and PhP(CH₂CH₂PPh₂)₂ in CH₂Cl₂ at room temperature afforded the dicarbonyl complex [MoCl(GeCl₃)(CO)₂{PhP(CH₂CH₂PPh₂)₂}] (8) in good yield.     

Palladium(II)‐ und Platin(II)‐Komplexe mit dem Antimalariamittel Mefloquin als Liganden

Metal Complexes of Biologically Important Ligands. CXXVI. Palladium(II) and Platinum(II) Complexes with the Antimalarial Drug Mefloquine as Ligand The coordination sites of the antimalarial drug mefloquine (L) were studied. Reactions of the chloro bridged complexes (allyl)Pd(μ‐Cl)₂Pd(allyl) and (R₃P)(Cl)M(μ‐Cl)₂M(Cl)(PR₃) (M = Pd, Pt) with racemic mefloquine give the compounds (allyl)(Cl)Pd(L) ( 1 ), Cl₂(Et₃P)Pt(L) ( 2 ) and Cl₂(Et₃P)Pd(L) ( 3 ) with coordination of the piperidine N atom of mefloquine. In the presence of NaOMe the N,O‐chelate complexes Cl(Et₃P)Pt(L–H⁺) ( 4 ) and Cl(R₃P)Pd(L–H⁺) ( 5 , 6 , R = Et, nBu) were obtained. Protection of the piperidine N atom of mefloquine by protonation allows the synthesis of the complexes Cl₂(Et₃P)Pt(L + H⁺) ( 7 ) in which mefloquine is coordinated via the quinoline N atom. The structures of 2 , 3 and 4 were determined by X‐ray diffraction analysis. In the crystal of 4 pairs of enantiomers are found which are linked by two hydrogen bridges between the amine group and the chloro ligand.     

Heterobinuclear and Heterotrinuclear complexes of Oxorhenium(V) with Cu(II), Ni(II), Fe(III), UO2(VI) and Th(IV) in the solid state

New heteronuclear complexes containing oxorhenium(V), Cu(II), Ni(II), Fe(III), UO₂(VI) and Th(IV) ions were prepared by the reaction of the complex ligand, [ReO(H₄L)Cl]Cl₂, where H₄L = 8,17-dimethyl-6,15-dioxo-5,7,14,16-tetrahydrodibenzo[a,h][14]annulene-2,11-dicarboxylic acid, with the previous transition and actinide salts. Three heteronuclear Cu(II) complexes were isolated depending on the ratio of [ReO(H₄L)Cl]Cl₂?:?Cu(II) ion. When the ratios were 1?:?0.5, 1?:?1 and 1?:?2, the heteronuclear complexes {[ReO(H₃L)Cl]₂CuCl₂(OH₂)₂}SO₄ · H₂O (I), [ReO(H₃L)Cl₂Cu(OH₂)₂(SO₄)] (II) and {ReO(H₂L)Cl[Cu(OH₂)₃ SO₄]₂} (III) were obtained, respectively. Heteronuclear complexes of the other metal cations were obtained by mixing [ReO(H₄L)Cl]Cl₂ with the metal salt in the ratio 1?:?1 to obtain the heteronuclear complexes [ReO(H₃L)Cl₂Ni(OH₂)₂](NO₃)₂ (IV), [ReO(H₃L)Cl₃Fe(OH₂)₃](NO₃)₂ (V), [ReO(H₃L)ClUO₂(NO₃)₂ (OH₂)]Cl (VI) and [ReO(H₃L)Cl₃Th(NO₃)₂(OH₂)]NO₃ · 2H₂O (VII). The complex ligand coordinates with the heterometal ion via the carboxylate group, and the infrared bands ν_as COO and ν_s COO indicate that the carboxylate acts as a unidentate ligand to the heterometal cations. Cu(II) and Fe(III) cations in the heteronuclear complexes have octahedral geometry, while Ni(II) is square planar. Thermal studies explored the possibility of obtaining new heteronuclear complexes pyrolytically in the solid state from the corresponding mother complexes. The structures of the complexes were elucidated by conductance, IR and electronic spectra, magnetic moments, ¹H NMR and TG-DSC measurements as well as by mass spectroscopy.     

Haloalkyl complexes of the transition metals: IV. The formation of a cationic ylide complex of platinum(II) from a chloromethylplatinum(II) complex and the crystal structures of cis-[Pt(CH2PPh3)X(PPh3)2]I (X = Cl or I)

The reactions of Pt(PPH₃)₄ and Pt(C₂H₄)(PPh₃)₂ with CH₂ClI have been investigated. The product of the reaction of Pt(PPh₃)₄ with CH₂ClI is the cationic ylide complex cis-[Pt(CH₂PPh₃)Cl(PPh₃)2][I], whereas the reaction of Pt(C₂H₄)-(PPh₃)₂ gives the oxidative addition product Pt(CH₂Cl)I(PPh₃)₂. Reaction of cis- or trans-Pt(CH₂Cl)I(PPh₃)₂] with PPh₃ gives the complex cis-[Pt(CH₂PPh₃)-Cl(PPh₃)₂][I]. The structures of the complexes cis-[Pt(CH₂PPh₃X(PPh₃)₂][I] (where X = Cl or I) have been determined by X-ray crystallography. Both complexes crystalize in the monoclinic space group P2₁/n. For X = Cl a 1388.6(7), b 2026.7(10), c 1823.9(9) pm, β 96.51(2)° and R converged to 0.075 for 3542 observed reflections; structural parameters Pt-Cl 240(1), Pt-C(3) 212(2), Pt-P(2) (trans to Cl) 235(1) and Pt-P(1) (trans to CH₂PPh₃) 233(1) pm; Cl-Pt-C(3) 86.9(5), C(3)-Pt-P(2) 91.8(5), P(2)-Pt-P(1) 97.0(2) and P(1)-Pt-Cl 85.1(2)°. For X = I, a 1379.4(7), b 2044.4(10), c 1840.0(9) pm, β 96.09(2)° and R converged to 0.071 for 4333 observed reflections; structural parameters Pt-I 266(1), Pt-C(3) 212(2), Pt-P(2) (trans to I) 226(1) and Pt-P(1) (trans to CH₂PPh₃ 233(1) pm; I-Pt-C(3) 87.2(5), C(3)-Pt-P(2) 91.5(5), P(2)-Pt-P(1) 96.5(2) and P(1)-Pt-I 85.6(1)°. Some other complexes of the type cis-[Pt(CH₂PPh₃)X(PPh₃)₂]Y are also described.     

3-(2-吡啶基)-1,2,4-三唑配体Co(II)Cu(II)和Cd(II)配合物的合成、结构及荧光性质

利用3-（2-吡啶基）-1,2,4-三唑配体（HL）和不同的金属盐设计合成了5个配合物[Co（HL）₂（H₂O）₂]（NO₃）₂（1）、[Cu₂（L）₂（NO₃）₂（H₂O）₄] （2）、[Cu₂（L）₂（AcO）₂（H₂O）₂]·6H₂O （3）、[Cu₂（L）₂（HL）₂（ClO₄）₂]·2CH₃CN （4）和[Cd₂（L）₂（HL）₂（NO₃）₂]·2H₂O （5）,并通过X射线单晶衍射、红外、元素分析、X射线粉末衍射和热重对配合物结构进行了表征。测试结果表明配合物1具有单核结构,并且可以通过氢键的相互作用形成二维超分子结构。配合物2~5为双核结构。配合物2和5可以通过氢键的相互作用形成二维超分子结构。配合物3通过氢键的相互作用形成三维超分子结构。研究了配合物中HL配体的配位模式。此外,研究了配体HL和配合物1和5的固态荧光性质及荧光寿命。