Nickel(II) di(pentyl)dithiocarbamates with P ligands

Ni(II) di(pentyl)dithiocarbamates of composition [Ni(Pe₂dtc)₂], [NiX(Pe₂dtc)(PPh₃)] (X = Cl, Br, I, NCS), [Ni(NCS)(Pe₂dtc)(PBut₃)], [Ni(Pe₂dtc)(PPh₃)₂]ClO₄ and [Ni(Pe₂dtc)(PPh₃)₂]PF₆ (Pe₂dtc = di(pentyl)dithio-carbamate, PPh₃ = triphenylphosphine, PBut₃ = tributylphosphine) have been synthesized. The complexes have been characterized by the usual methods. X-ray structure analyses confirmed the nature of [NiI(Pe₂dtc)(PPh₃)] and [Ni(Pe₂dtc)(PPh₃)₂]ClO₄ complexes.     

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].     

Cationic (fluoromesityl)palladium(II) complexes

Halide abstraction from [Pd(μ-Cl)(Fmes)(NCMe)]₂ (Fmes = 2,4,6-tris(trifluoromethyl)phenyl or nonafluoromesityl) with TlBF₄ in CH₂Cl₂/MeCN gives [Pd(Fmes)(NCMe)₃]BF₄, which reacts with monodentate ligands to give the monosubstituted products trans-[Pd(Fmes)L(NCMe)₂]BF₄ (L = PPh₃, P(o-Tol)₃, 3,5-lut, 2,4-lut, 2,6-lut; lut = dimethylpyridine), the disubstituted products trans-[Pd(Fmes)(NCMe)(PPh₃)₂]BF₄, cis-[Pd(Fmes)(3,5-lut)₂(NCMe)]BF₄, or the trisubstituted products [Pd(Fmes)L₃]BF₄ (L = CN^tBu, PHPh₂, 3,5-lut, 2,4-lut). Similar reactions using bidentate chelating ligands give [Pd(Fmes)(L-L)(NCMe)]BF₄ (L-L = bipy, tmeda, dppe, OPPhPy₂-N,N′, (OH)(CH₃)CPy₂-N,N′). The complexes trans-[Pd(Fmes)L₂(NCMe)]BF₄ (L = PPh₃, tht) (tht = tetrahydrothiophene) and [Pd(Fmes)(L-L)(NCMe)]BF₄ (L-L = bipy, tmeda) were obtained by halide extraction with TlBF₄ in CH₂Cl₂/MeCN from the corresponding neutral halogeno complexes trans-[Pd(Fmes)ClL₂] or [Pd(Fmes)Cl(L-L)]. The aqua complex trans-[Pd(Fmes)(OH₂)(tht)₂]BF₄ was isolated from the corresponding acetonitrile complex. Overall, the experimental results on these substitution reactions involving bulky ligands suggest that thermodynamic and kinetic steric effects can prevail affording products or intermediates different from those expected on purely electronic considerations. Thus,water, whether added on purpose or adventitious in the solvent, frequently replaces in part other better donor ligands, suggesting that the smaller congestion with water compensates for the smaller M-OH₂ bond energy.     

Synthesis of organometallic hydrotris(pyrazol-1-yl)boratoruthenium(II) complexes

The reactions of K[HB(pz)₃] (pz = pyrazol-1-yl) with the coordinatively unsaturated σ-vinyl complexes [Ru(CRCHR)Cl(CO)(PPh₃)₂] (R = H, Me, C₆H₅) proceed with loss of a chloride and a phosphine ligand to provide the compounds [Ru(CRCHR)(CO)(PPh₃){HB(pz)₃}] in high yield. Similar treatment of the complex [Ru(C₆H₄Me-4)Cl(CO)(PPh₃)₂] leads to the related σ-aryl derivative [Ru(C₆H₄Me-4)(CO)(PPh₃){HB(pz)₃}] whilst the complex [RuClH(CO)(PPh₃)₃] treated successively with diphenylbutadiyne and K[HB(pz)₃] provides the unusual derivative [Ru{C(CCPh)CHPh}(CO)(PPh₃){HB(pz)₃}].     

The solid state chemistry of dichlorobis(pyridine)manganese(II) and dichlorobis(pyridine)nickel(II)

Summary The thermal decompositions of [MnCl₂(py)₂] and [NiCl₂(py)₂] were investigated and the following dissociation reactions were observed: [MnCl₂(py)₂](s)MnCl₂(py)(s)+(py)(g) [MnCl₂(py)₂](s)MnCl₂(s)+2(py)(g) and [NiCl₂(py)₂](s)NiCl₂(py)(s)+(py)(g) [NiCl₂(py)₂](s)NiCl₂(s)+2(py)(g). Quantitative thermodynamic as well as kinetic data were obtained by performing dynamic and isothermal studies on the complexes. The DSC studies provided evidence for the existence of the additional intermediates [Ni₃Cl₆(py)₂] and [Mn₃Cl₆(py)₂], which could not be obtained from the dynamic and isothermal studies.     

Reactions of benzylchlorobis(triphenylphosphine)palladium(II) with dimethyl acetylenedicarboxylate

Benzylchlorobis(triphenylphosphine)palladium(II) reacted with dimethyl acetylenedicarboxylate to give [Pd[C(CO₂Me)=C(CH₂Ph)(CO₂Me)]Cl(PPh₃)₂] (II) and [(Ph₃P)ClPdμ-C(CO₂Me)=C(CO₂Me)PdCl(PPh₃) (III). Complexes II and III reacted with Tl(acac) to afford [PdC(CO₂Me=C(CH₂Ph)(CO₂Me)-(acac)(PPh₃)] and [(Ph₃P)(acac)Pdμ-C(CO₂Me)=C(CO₂Me)Pd(acac)(PPh₃)], respectively.     

Monocarbonyl cationic rhodium(I) complexes

Summary The preparations and characterisation of cationic complexes of the type [Rh(CO)(MeCN)(PR₃)₂]ClO₄, [Rh(CO)L(PR₃)₂]ClO₄ (L=py or 2-MeOpy), [Rh(CO)(L-L)(PR₃)₂]ClO₄ (L-L = bipy or phen) and [Rh(CO)(PR₃)₃]ClO₄ with PR₃ = P(p-YC₆H₄)₃ (Y=Cl, F, Me or MeO) are described.     

Transition Metal Complexes with Bidentate Ligands Spanning trans-Positions. VIII. The reactions of the nucleophile trans-[RuCl(NO)(1)] (1 = 2,11-bis(diphenylphosphinomethyl)benzo[c]-phenanthrene) with carbon monoxide and the phosphite ligand (2) (2 = 1-ethyl-3,5,8-trioxa-4-phosphabicyclo (2.2.2)octane)

The preparation of the nucleophile trans-[RuCl(NO)( 1 )], where 1 is the bidentate ligand Ph₂PCH₂C₁₈CH₂PPh₂, and of the five-coordinate species [RuCl(CO)(NO)( 1 )], [RuCl(CO)(NO)(Ph₂PCH₂Ph)₂] and [RuCl(NO)( 2 )( 1 )] are reported. The crystal structure of [RuCl(CO)(NO)( 1 )] shows that the coordination around the metal atom is distorted trigonal bipyramidal with the phosphorus atoms in axial positions. The Ru? N? O bond angle is 142.8°. ¹H- and ³¹P-NMR. and \documentclass{article}\pagestyle{empty}\begin{document}$ \tilde \nu $\end{document}_NO IR.-data for the above complexes are reported and related to the coordination geometry.     

Synthesis and crystal structure of hexakis(isothiocyanato)erbium(III) thiocyanate bis(18-crown-6)dipotassium bis[(18-crown-6)ethanolpotassium]

A new complex compound, [K₂(18-crown-6)₂[K(18-crown-6)(EtOH)]₂[Er(NCS)₆](SCN) (I), was synthesized and its crystal structure was studied by X-ray diffraction. In this work, the synthes and X-ray difraction stady of the crystals of a new complex, hexakis (isothiocyanato) erbiu(III) thiocyanate bis(18-crown-6) dipotassium bis(18-crown-6) ethanolpotassium], [K₂(18-crown-6)₂][K(18-crown-6)(ETON)]₂[Er(NCS)₆(SCN)(I)] are described. In crystal I, the alternating [Er(NCS)₆]^3? anions and binuclear complex cation [K(18-crown-6)₂]²⁺ from infinite chains via the F-S bonds, while two complex cations [K(18-crown-6)(ETON)]⁺ and the statistically disordered SCN^? anion between them are linked by the hydragen bonds O-H…S and O-H…N. Complex I contains the host-guest complex cations [K₂(18-crown-6)₂)]²⁺ and [K(18-crown-6)(ETON)]⁺ [1]. The alternating octabedral [Er(NCS)₆]^3? anions and binuclear complex cations [K₂(18-crown-6)₂]²⁺of crystal I form infinite chains via the K-S bonds, while two complex cations [K(18-crown-6)(EtOH)]⁺ and the statistically disordered SCN^? anion lying between them are linked by interionic hydrogen bonds O-H…S and O-H…N. Complex I contains the host-guest complex cations [K₂(18-crown-6)₂]²⁺ and [K(18-crown-6)(EtOH)]⁺ [1].     

Modifizierung von Schichtsilicaten mit sterisch anspruchsvollen Metallkomplexen. 3. Synthese und Intercalation der planar-quadratischen Komplexe [Cu(bppep)(H2O)](ClO4)2 und [Ni(bppep)(Cl)Cl] (bppep = 2,6-Bis[1-phenyl-1-(pyridin-2-yl)ethyl]pyridin) in Hectorit

Modification of Layer Silicates by Sterically Demanding Metal Complexes: Synthesis and Intercalation of the Square Planar Complexes [Cu(bppep)(H₂O)](ClO₄)₂ and [Ni(bppep)(Cl)]Cl (bppep = 2,6-Bis[1-phenyl-1-(pyridine-2-yl)ethyl]pyridine) in Hectorite Sodium-aqua hectorite reacts with [Cu(bppep)(H₂O)](ClO₄)₂ and [Ni(bppep)(Cl)]Cl with exchange of the sodium-aqua cations against the complex cations [Cu(bppep)(H₂O)]²⁺ and [Ni(bppep)(Cl)]⁺, respectively. In addition, cation-anion pairs of [Cu(bppep)(H₂O)](ClO₄)₂ and [Ni(bppep)(Cl)]Cl are also intercalated between the hectorite layers (intersalation). On the other hand, it is possible to synthesize [Cu(bppep)(H₂O)]²⁺ or [Ni(bppep)(H₂O)]²⁺ modified hectorites without additional ion-pair intercalation (intersalation) by reaction of nickel- and copper-hectorites with the bppep ligand.     

Unusual sandwich platinum(II) complex: [Pt(phen)2]2+ cation between two Pt(phen)(OOCMe)2 molecules

New carboxylate platinum(II) complexes: syn and anti isomers of Pt(phen)(OOCMe)₂ molecular complex, [Pt(phen)(NCMe)₂](O₃SCF₃)₂, as well as unusual sandwich complex [Pt(phen)₂]²⁺ · 2syn-[Pt(phen)(OOCMe)₂] where [Pt(phen)₂]²⁺ cation is inserted between two syn-Pt(phen)(OOCMe)₂ molecules were synthesized and structurally characterized by X-ray diffraction analysis. As distinct from syn- and anti-Pt(phen)(OOCMe)₂ and [Pt(phen)(NCMe)₂](O₃SCF₃)₂ complexes with flat phenanthroline ligand, the phen ligands in [Pt(phen)₂]²⁺ cation have a curved configuration. Comparative DFT analysis of geometry of model structures phen, phen⁺, phenH⁺, and [Ptphen₂] ⁿ⁺ (n = 1, 2) showed that electron removal from phen molecule had no effect on its geometry in both free state and platinum(II) complexes.     

Cyclometallation of a pyrrole ring of 2-(1-pyrrolyl)pyridine with palladium(II) and rhodium(III)

2-(1-Pyrrolyl)pyridine (Hplp) is cyclometallated with lithium tetrachloropalladate(II) and hexahalogenotetrakis(tri-n-butylphosphine)dirhodium(III) to give [PdCl(plp)]₂ and [RhX₂(plp(PBu₃)₂] (X = Cl, Br; PBu₃ = tri-n-butylphosphine), respectively, where deprotonated plp is coordinated via the pyridine-N and pyrrole-2C atoms forming a five-membered metallacycle. [PdCl(plp)]₂ reacts with pyridine (py) and with PBu₃ to form the adducts [PdCl(plp)L] (L = py, PBu₃) and with acetylacetone (Hacac) to afford the complex [Pd(plp)(acac)]. Metathesis of [RhCl₂(plp)(PBu₃)₂] with excess lithium iodide gives a mixed halogeno complex [RhClI(plp)(PBu₃)₂]. These complexes are characterized spectroscopically.     

The interaction of an osmium-carbon triple bond with copper(I), silver(I) and gold(I) to give mixed dimetallocyclopropene species and the structures of Os(AgCl) (CR) Cl(CO) (PPh3)2

The osmium carbyne complex, Os(CR)Cl(CO)(PPh₃)₂, (R  p-tolyl) reacts with Group I halides to form the mixed dimetallocyclopropene species, $\text{Os(Cul)(C}$R)Cl(CO)(PPh₃)₂, $\text{Os(AgCl)(C}$R)Cl(CO)(PPh₃)₂, $\text{Os(AuCl)(C}$R)Cl(CO)(PPh₃)₂, and [$\text{Os[Ag(OClO}{}_3\text{)](C}$R)Cl(CO)(MeCN)(PPh₃)₂] ClO₄ X-ray crystal structure determination of $\text{Os(AgCl)(C}$R)Cl(CO)(PPh₃)₂ confirms the presence of a three-membered ring and the structure can be viewed as the “acetylene-like” interaction of an osmium—carbon triple bond with AgCl. In acid solution AgCl is precipitated and an alkylidene complex results from proton addition to the carbyne ligand.     

Copper(II) oxalate and oxamate complexes

Reaction of Cu^II salts with phenanthroline and oxalate (ox) or oxamate (oxm) gives [Cu(phen)(ox)(H₂O)] · H₂O or [Cu(phen)(oxm)(H₂O)] · H₂O complexes while direct treatment of Cu^II salts with oxalate or oxamate gives [NH₄]₂[Cu(ox)₂] and [Cu(oxm)₂(H₂O)₂] respectively. The X-ray structures of one example of each system, aquo-oxamato-phenanthroline-copper(II)-dihydrate and the polymeric ammonium-bis(aquo)-tetraoxalato-dicopper(II)-dihydrate, are reported.     

Kinetics and mechanism of acid and base hydrolysis ofcis-chloro-(benzotriazole)bis(ethylenediamine)cobalt(III) andcis-chloro-(N-methylbenzotriazole)bis(ethylenediamine)cobalt(III) cations

Summary The kinetics of acid hydrolysis ofcis-[CoCl(btzH)(en)₂]²⁺ andcis-[CoCl(btzMe)(en)₂]²⁺ complexes (where btzH = benzotriazole, btzMe =N-methylbenzotriazole and en = ethylenediamine) have been investigated in HClO₄ at ionic strength 1 = 0.25 mol dm^–3 in the 30–40° range. In the 1.0 x 10^–1 to 1.0 X 10^–3 mol dm^–3 acid strength range, the rate of aquation of the [CoCl(btzH)(en)₂]²⁺ cation follows the relationship:-d ln[complex]/dt = k₁ + k₂K_NH[^H+]^–1, where k₁ and k₂ are aquation rate constants of the acid independent and acid dependent steps respectively, and K_NH is the acid dissociation constant of the coordinated benzotriazole.cis-[CoCl(btzMe)-(en)₂]²⁺ undergoes acid independent hydrolysis presumably due to the absence of a labile N-H proton. The base hydrolysis could be followed for thecis-[CoCl(btzMe)(en)₂]²⁺ complex only by measuring hydrolysis rates at 0°.     

Inhibitorial effect of the Cu(II) and Ni(II) complexes with polyamines and imidazole derivatives on the Ca,Mg-dependent ATP-ase substrate

The investigation of the inhibitory activity on the Ca,Mg-dependent ATP-ase substrate of some Cu(II) and Ni(II) complexes with polyamines and imidazole derivatives is reported. These results show that the Cu(II) complexes have high inhibitorial effect with the exception of the following very stable compounds: square planar [Cu(N-PropIm)₂(NCS)₂], distorted octahedral [Cu(bipy)₂(NCS)₂] and five coordinate [Cu(Me₆tren)(NCS)] (SCN). The Ni(II) derivatives present a medium inhibitorial activity except to the stable tetrahedral [Ni(N-PropIm)₂(NCS)₂], hexacoordinate [Ni(dpt)(tn)(NCS)] (SCN) and fivecoordinate [Ni(dpt)(tn)]Br₂ and [Ni(Me₆tren)(NCS)] (SCN). An explanation of these conclusions is reported.     

Carbonylation of diamino-ligated methylpalladium(II) methoxide complexes

The methylpalladium(II) methoxide complexes [Pd(Me)(OMe)(N∼N)] (N∼N)=tmeda or bpy) have been synthesized by alkoxidemethanol exchange of [Pd(Me)(OCH)(CF₃)₂)(N∼N)] in MeOH. The bpy complex undergoes insertion of CO to give either a methyl(methoxycarbonyl) complex [Pd(Me)(CO₂Me)(bpy)] (at −60°C) or an acyl(methoxycarbonyl) complex [Pd(COMe)(CO₂Me)(bpy)] (at −25°C). Both carbonylated species were isolated and characterized at low temperature.     

二(三苯基膦)乙基黄原酸金属配合物的晶体结构和谱学表征

0IntroductionTheincreasingcommercialvalueoftransitionmetalcomplexesofxanthateshasarousedconsiderableinterestingintheirchemistry.Whiletheiranalyticalapplicationsarewellknown犤1犦,theyarenowfindingextensiveuseinvulcanizationofrubber,frothfloatationprocessforconcentrationofsulphideores,asantioxi-dants,lubricants犤2,3犦,andhavebeenfoundtopossessfungicidalandinsecticidalactivity犤4犦.Inrecentyears,therehasbeengrowinginterestinthestudyofd10metalcomplexes,whichexhibitrichphotophysicalandpho-tochemica…     

Bis(diphenylphosphano)alkan- und 1-(Diphenylphosphano)-2-(2-pyridino)ethan-N-Arylsulfinylamin-Nickel(0)-Komplexe

Bis(diphenylphosphano)alkane- and 1-Diphenylphosphano-2-(2-pyridino)ethane-N-arylsulfinylamine Nickel(0) Complexes Synthesis and properties of the bis(diphenylphosphano)alkane-N-phenyl-sulfinylamine-nickel(0) complexes [Ni{Ph₂P(CH₂)_nPPh₂}(PhNSO)] (n = 2 dppe, n = 3 dppp, n = 4 dppb) as well as of the 1-(diphenylphosphano)-2-(2-pyridino)ethane nickel(0) complexes [Ni(dpppe)₂], [Ni(dpppe)(p-TolNSO)] and [Ni(dpppe)(PPh₃)₂] are described. These compounds have been characterized by i. r. and ³¹P n.m.r. spectroscopy. The N-arylsulfinylamine ligands are η²-(N, S)-side on coordinated.     

Six-membered cyclometallated derivatives of platinum(II) derived from 2-benzylpyridines. Crystal and molecular structure of [Pt(L)(Ph3P)Cl] (HL = 2-(1-methylbenzyl)pyridine)

The reaction of K₂[PtCl₄] with 2-(1-methylbenzyl)pyridine, HL, and 2-benzylpyridine, HL', affords the cyclometallated species [{Pt(L)Cl}₂] (1) and [{Pt(L')Cl}₂] (2), respectively. The chloride bridge in complex 1 can be split by neutral or anionic species to give the monomeric, [Pt(L)(Ph₃P)Cl], as two isomers, trans-P-Pt-C (3) and trans-P-Pt-N, (4), [Pt(L)(py)Cl] (5), [Pt(L)(CO)Cl] (6), [Pt(L)(CNCH₂SO₂C₆H₄CH₃-4)Cl] (7), [Pt(L)(acac)] (Hacac = 2,4-pentanedione) (8), [Pt(L)(dppm)][BF₄] (dppm = bis(diphenyl-phosphino)methane) (9), [Pt(L)(dppe)][BF₄] (dppe = bis(diphenylphosphino)ethane) (10) and [Pt(L)(dipy)][BF₄](dipy = 2,2'-dipyridine) (11). Similarly, compound 2, by reaction with Ph₃P, affords [Pt(L')(Ph₃P)Cl], as two isomers, trans-P-Pt-C (12) and trans-P-Pt-N (13). Reaction of compounds 1 or 4 with AgBF₄ in acetonitrile affords [Pt(L)(CH₃CN)₂IBF₄] (14) or [Pt(L)(Ph₃P)-(CH₃CN)][BF₄] (15). From these, [Pt(L)(Ph₃P)₂][BF₄] (16), [Pt(L)(Ph₃P)(CO)][BF₄] (17) and [Pt(L)(Ph₃P)(py)][BF₄] (18), can be obtained by displacement of the coordinated acetonitrile. The new complexes were characterized by IR, ¹H and ³¹P NMR and FAB-MS spectroscopic techniques. The NMR spectra at room temperature of most of the species derived from HL give evidence for the presence in solution of two diastereomers a and b. The structure of one diastereomer of complex 4 has been solved by single crystal X-ray diffraction, 4b. The platinum atom is in an almost square planar geometry with a P-Pt-N trans arrangement: Pt-N = 2.095(3), Pt-C = 1.998(4), Pt-P = 2.226(1) and Pt-Cl = 2.400(1) Å. The six-membered cyclometallated ring is in a boat conformation, with the CH₃ group in an equatorial position, i.e pointing away from the metal. Attempts to obtain [{Pt(L″)Cl}₂] (HL″ = 2-(dimethylbenzyl)pyridine), afforded an insoluble product heavily contaminated by platinum metal; treatment of this crude material with Ph₃P gave [Pt(L″)(Ph₃P)Cl] (19).