Diarsine Ligands Research Articles

Cover Feature: Dinuclear Gold(I) Chloride Complexes with Diarsine Ligands (Eur. J. Inorg. Chem. 3/2021)

The Cover Feature shows dinuclear gold(I) chloride complexes with a series of diarsine ligands. The length and flexibility of the linkers between the two arsenic atoms were varied. The conformations and emission properties of the complexes were highly dependent on the ligand structures. In addition, the emission color and intensity of the complexes were drastically changed by external stimuli such as grinding and cooling. More information can be found in the Full Paper by H. Imoto, K. Naka and co-workers.

Dinuclear Gold(I) Chloride Complexes with Diarsine Ligands

Recently, we have developed synthetic methods for preparing diarsenic ligands. Herein, dinuclear gold(I) chloride complexes with various kinds of diarsenic ligands [Au2Cl2(diars)] were synthesized (diars = dpae, dpap, dpab, cis‐dpav, trans‐dpav, dpapz, and dpaq). X‐ray crystallography revealed that they can form intra‐ or intermolecular aurophilic interactions depending on the ligand structure except for dpab. Crystal polymorphs of Au2Cl2(dpae) and Au2Cl2(dpap) were observed because of the flexible alkylene linkers of the diarsine ligand. The emission behaviors of the complexes were drastically changed by the ligands, which should affect the energy barrier for internal conversion from the intraligand excitation state to the halide‐to‐ligand charge transfer one. Some of the complexes accordingly showed luminescent mechanochromism and/or thermochromism.

Pentagonal bipyramidal complexes of WOCl4 and WSCl4 with diphosphine and diarsine ligands

The seven-coordinate tungsten(VI) complexes, [WOCl4{o-C6H4(EMe2)2}] and [WSCl4{o-C6H4(EMe2)2}] (E = P, As), have been prepared by reaction of WOCl4 or WSCl4 with the ligands in anhydrous CH2Cl2 or toluene, and fully characterised by microanalysis, IR, 1H and 31P{1H} NMR spectroscopy. The X-ray crystal structures of [WOCl4{o-C6H4(AsMe2)2}] and [WSCl4{o-C6H4(PMe2)2}] have been determined and revealed pentagonal bipyramidal geometries with axial O/Cl or S/Cl. Attempts to isolate similar complexes with o-C6H4(PPh2)2, PMe3 or AsEt3 were unsuccessful, due to facile reduction of the tungsten centre. Several reduction products have also been identified crystallographically, including the tungsten (V) species, [WOCl3{o-C6H4(PMe2)2}], [WOCl3{o-C6H4(PMe2)(P(O)Me2)}] and [WCl4{o-C6H4(PPh2)2}2][WCl6].

Systematics of BX3 and BX2(+) Complexes (X = F, Cl, Br, I) with Neutral Diphosphine and Diarsine Ligands.

The coordination chemistry of the neutral diphosphines, R2P(CH2)2PR2 (R = Me or Et) and o-C6H4(PR'2)2 (R' = Me or Ph), and the diarsine, o-C6H4(AsMe2)2, toward the Lewis acidic BX3 (X = F, Cl, Br, and I) fragments is reported, including several rare complexes incorporating BF3 and BF2(+). The studies have revealed that the flexible dimethylene linked diphosphines form [(BX3)2{μ-R2P(CH2)2PR2}] exclusively, confirmed by multinuclear NMR ((1)H, (11)B, (19)F{(1)H}, and (31)P{(1)H}) and IR spectroscopy and microanalytical data. Crystallographic determinations of the four BX3 complexes with Et2P(CH2)2PEt2 confirm the 2:1 stoichiometry and, taken together with the spectroscopic data, reveal that the Lewis acid behavior of the BX3 fragment toward phosphine ligands increases in the order F ≪ Cl ∼ Br < I. The first diphosphine- and diarsine-coordinated dihaloboronium cations, [BX2{o-C6H4(EMe2)2}](+) (E = P, As), are obtained using the rigid, preorganized o-phenylene linkages. These complexes are characterized similarly, and the data indicate that the complexes with o-C6H4(AsMe2)2 are much more labile and readily decomposed than the phosphine analogues. X-ray crystallographic studies on [BX2{o-C6H4(PMe2)2}][BX4] (X = Cl, Br), [BI2{o-C6H4(PMe2)2}][I3], and [BCl2{o-C6H4(AsMe2)2}][BCl4] confirm the presence of distorted tetrahedral coordination at boron through a chelating diphosphine or diarsine and two X ligands, with d(B-P) revealing a similar increase in Lewis acidity down group 17. Comparison of d(B-P) and d(B-As) reveals an increase of ca. 0.08 Å from P to As. Reaction of BCl3 with the diphosphine dioxide Ph2P(O)CH2P(O)Ph2 gives the ligand-bridged dimer [(BCl3)2{Ph2P(O)CH2P(O)Ph2}], while using either BF3 gas or [BF3(SMe2)] gives a mixture containing both [(BF3)2{μ-Ph2P(O)CH2P(O)Ph2}] and the unexpected difluoroboronium salt, [BF2{Ph2P(O)CH2P(O)Ph2}][B2F7] containing a chelating phosphine oxide. The structure of the latter was confirmed crystallographically.

Asymmetric synthesis of a chiral diarsine ligand via a cycloaddition reaction between 3,4-dimethyl-1-phenylarsole and diphenylvinylarsine

The organopalladium complex containing ortho-metallated (S)-[1-(dimethylamino)ethyl]naphthalene as a chiral auxiliary has been successfully employed to promote the asymmetric cycloaddition reaction between 3,4-dimethyl-1-phenylarsole and diphenylvinylarsine. In the intramolecular cycloaddition reaction, a pair of separable diastereomeric palladium complexes was obtained in the ratio of 6:1. The chiral naphthylamine auxiliary could be removed chemoselectively from the template by treatment with HCl and subsequently NaI to generate the neutral diiodo complex [(As–As)PdI2]. Treatment of the diiodo complex with KCN gave the enantiomerically pure As–As bidentate ligand in quantitative yield. In contrast to the reported similar P–P and As–P analogues, both arsenic donors in the diiodo complex could be readily eliminated to produce a structurally novel dimetallic complex.

Chemiluminescence from osmium(ii) complexes with phenanthroline, diphosphine and diarsine ligands

The reaction of various [Os(L)(2)(L')](2+) complexes (where L and L' are phenanthroline, diphosphine or diarsine ligands) and organic reducing agents after chemical or electrochemical oxidation of the reactants produces an emission of light corresponding to MLCT transitions. In certain instances, the emission was greater than that of [Ru(bipy)(3)](2+), but the relative signals were dependent on many factors, including reagent concentration, mode of oxidation, reducing agent and the sensitivity of the photodetector over the wavelength range.

Barometric Sensitive Coatings Based upon Osmium Complexes Dissolved in a Fluoroacrylic Polymer

Pressure sensitive paints (PSP) that measure the changes in air pressure have proved to be useful in the design of aircraft and other vehicles. In this study we incorporate highly luminescent divalent osmium complexes into PSP. The divalent osmium complexes were heptafluorobutyrate salts of [Os(N-N)2(L-L)]2+ or [Os(L-L)2(N-N)]2+, where N-N is a derivative of 1,10-phenanthroline, and L-L is a diphosphine or diarsine ligand. The complexes were dissolved into poly(1,1,1,3,3,3-hexafluoroisopropylmethacrylate-co-1H,1H-dihydroperflurobutylmethacrylate) (FIB) at a concentration of 0.002 g of complex to 1.000 g of polymer. The luminescence of the coatings was tested for pressure sensitivity, temperature dependence, and photodegradation. The paints featured strong pressure response, and the temperature dependence of the luminescence was measured as low as -0.11% degrees C(-1). Several of the complexes exhibited little photodegradation upon prolonged exposure to 400 nm light. These attributes make the complexes very desirable luminescent dyes for PSP.

Molecular and Crystal Structures of Pentafluorophenyl‐platinum(II) Complexes with Bis(diphenylphosphino)methane, Bis(diphenylarsino)methane and 1,2‐Bis(diphenylarsino)ethane

AbstractThe X‐ray crystal structures of [PtCl2(dppm)], [Pt(C6F5)2L] (L = dppm (bis(diphenylphosphino)methane), dpam (bis(diphenylarsino)methane), dpae (bis(diphenylarsino)ethane)) and [PtCl(C6F5)(dpae)] show the complexes to be monomeric with chelating dipnictido ligands, and not alternatives with bridging ligands. In [Pt(C6F5)2(dpam)2], there are two unidentate diarsine ligands in a cis‐arrangement.

Fac,trans-

The crystal structure of the heterobimetallic title compound, [ReRuCl(C(10)H(16)As(2))(2)(C(10)H(8)N(2))(2)(CO)(3)](PF(6))(2). 2C(3)H(6)O, is described. Both metal centres have pseudo-octahedral coordination geometries, with a facial arrangement of the carbonyl ligands at Re(I) and a trans disposition of the diarsine ligands at Ru(II). The dihedral angle between the pyridyl rings of the 4, 4'-bipyridine bridging ligand is 13.9 (6) degrees.

Coordination behaviour of diphosphine and diarsine oxides in four organotin(IV) adducts

Four new molecular adducts of diphenyl- and triphenyl-tin(IV) nitrates with 1,2-bis(diphenylarsoryl)ethane (dpaoe), bis(diphenylphosphoryl)methane (dppom) and trans-1,2-bis(diphenylphosphoryl)ethylene (tdppoet) have been synthesised and characterized by infrared spectroscopy, and an X-ray diffraction study has been carried out on two of them, {SnPh 3NO 3} 2dpaoe ( 1) and SnPh 2(NO 3) 2dppom ( 2). Both 1 and 2 crystallize in the triclinic space group P 1 , with unit-cell dimensions. 1: a 12.810(8), b 11.938(6), c 10.394(4) Å, α 97.92(4), β 90.00(5), γ 111.13(4)°, Z = 1, R = 0.0454; 2: a 13.845(6), b 13.119(4), c 10.444(6) Å, α 106.50(4), β 101.24(4), γ 91.33(4)°, Z = 2, R = 0.0504. The structure of 1 consists of binuclear monomeric units in which each tin atom is bound in a trigonal bipyramidal configuration to three phenyl rings in the equatorial plane and to the diarsine ligand and the nitrate group in the axial positions. In compound 2 the tin atom exhibits a pentagonal-bipyramidal coordination geometry with five oxygen atoms, two from the chelating dppom ligand and three from the two nitrate groups, around the pentagonal girdle, and the two phenyl groups at the apices of the bipyramid. The vibrational frequencies of the nitrate groups and of the diarsine and diphosphine ligands are discussed in the light of the X-ray results.

Synthesis and structural characterization of two arsine complexes of silver(I)

The syntheses and X-ray crystal structures of Ag(AsPh 3) 3Cl · 0.5CH 3COCH 3 ( 1) and of (AgNO 3) 2(Ph 2AsCH 2CH 2AsPh 2) ( 2) are described. The crystal structure of 1 contains discrete monomeric Ag(AsPh 3) 3Cl units in which Ag is tetrahedrally surrounded by three As atoms and one Cl atom, along with solvating acetone molecules. Compound 2 exists in the crystalline form as polymeric layers, since the diarsine ligand bridges the two independent silver atoms to form a dimer and the dimers are held together in layers through connecting nitrate groups. Carbon atoms of adjacent phenyl rings complete the environment of both the silver atoms and aid in binding the molecules together.

Structural characterization of a binuclear tin adduct: µ-[1,2-bis(diphenylarsoryl)ethane-O:O′]-bis(chlorotriphenyltin)

The crystal structure of the title compound (SnPh3Cl)2[Ph2As(O)CH2CH2(O)AsPh2] has been determined by X-ray diffraction. About tin, the geometry is essentially trigonal bipyramidal, the chloride ion and the diarsine ligand occupying the axial positions, with the aromatic rings in the equatorial plane.

Diphenylarsinoderivate des Maleins�ureanhydrids und verwandte Verbindungen. Kristall- und Molek�lstruktur des 2,3-Bis(diphenylstibino)maleins�ureanhydrids

The unusual properties of bis(diphenylphosphino)maleic anhydride and similar ditertiary phosphines has prompted the synthesis of analogous arsines and stibines. Bis(diphenylarsino)maleic anhydride,-maleic thioanhydride and-N-methyl maleic imide, bis(diphenylstibino)maleic anhydride (5) and-maleic thioanhydride are obtained as crystalline yellow or red compounds by the reaction of the corresponding 2,3-dichloromaleic acid derivatives with diphenyl(trimethylsilyl)arsine and-stibine resp. The uv/vis spectra and characteristic i.r. bands of selected compounds are given and compared with those of the corresponding phosphines. The strong shift of νC=C to lower wavenumbers observed in all compounds has caused the determination of crystal and molecular structure of5 by x-ray diffraction. Bond distances and angles are given. The complex formation of the new diarsine ligands has been examined by the preparation of Ni-, Cr- and Mo-carbonyl derivatives. As the first organylsulfane substituted maleic acid derivatives bis(phenylthio)maleic thioanhydride,-N-methyl-maleic imide and-maleic acid dimethylester are synthesized and described.

Trans-Chelation of 1,12-bis(dimethylarsino)dodecane to palladium(II)

The diarsine ligand, 1,12-bis(dimethylarsino)dodecane, reacts with tetrachloropalladate(II) in ethanol/dichloromethane to form in highly yield the monomeric [Pd(ligand)Cl 2] complex containing the trans-chelating diarsine.

Complexes of osmium halides with monodentate and bidentate ligands

Complexes of osmium halides with donor ligands L (L = PPh 3, AsPh 3, SbPh 3, PMePh 2, C 2H 4(AsPh 2) 2, PPr 2 n Ph, CH 2(AsPh 2) 2) have been prepared. The IR and NMR spectra of complexes of the type trans-[OsCl 4L 2], fac-[OsX 3L 3] and trans-[OsX 2L 4] are recorded and discussed. For the trans complexes the halogen sensitive modes occur near those of the related [OsX 4] 2− species. Tentative assignments for ν(OsY) (Y = P, As, Sb) are discussed on the basis of the experimental results. Raman and ESR spectra of selected complexes have been recorded and are discussed. NMR data indicates the presence of monodentate diarsine ligands in trans- (OsCl 4(CH 2(AsPh 2) 2) 2)·C 2H 5OH.

ChemInform Abstract: COMPLEXES BETWEEN FLUORO(DITERTIARY ARSINES) AND METAL TETRAHALIDES

AbstractDer Einfluß von F‐Atomen in tert.‐Diarsinen auf ihre Reaktionen mit Metall‐halogeniden wird untersucht.

Trans-bidentate behaviour of a potentially tetradentate ligand to palladium(II) and platinum(II)

The ligand 1,3-bis(3-dimethylarsinopropylthio)propane, L, forms MLX 2 (M  Pd, Pt; X  Cl, Br, I), which are pentacoordinate [MLX]X in the solid state and in nitromethane and planar trans-[MLX 2], containing a trans-chelating diarsine ligand in dichloromethane; these are the first examples of a potentially tetradentate ligand acting as a trans-chelating bidentate.

Complexes between fluoro(ditertiary arsines) and metal tetrahalides

The influence of incorporating fluorine atoms into ditertiary arsines on the reactions of the latter with metal halides has been investigated. The fluoroalicyclic-bridged ligands, 1,2-bis(dimethylarsino)-3,3,4,4-tetrafluorocyclobutene and 1,2-bis(dimethylarsino)-3,3,4,4,5,5-hexafluorocyclopentene, and the fluoroaromatic-bridged ligands, 1,2-bis(dimethylarsino)-3-fluorobenzene and 1,2-bis(dimethylarsino)-4-fluorobenzene, form six-co-ordinate complexes [MX4(diarsine)](M = Ti, V, Mo, Re, or Sn; X = Cl or Br). Eight-co-ordinate dodecahedral bis adducts are formed only with niobium tetrachloride and tetrabromide, and with the last three diarsine ligands. Complexes with nickel(II) and iron(II) confirm that these fluorodiarsines are weaker donors than are conventional diarsine ligands.

Bidentate group VB chelates, Part VII. Some palladium(II) complexes with diphosphine, phosphine-arsine, and diarsine ligands, including some thiocyanate derivatives

Eighteen complexes of palladium(II) salts and the bidentate chelating ligands cis-1,2-bis(diphenylphosphino)ethylene (vpp). cis-1,2-bis(diphenylarsino)ethylene (vaa), cis-1-diphenylarsino-2-diphenylphosphinoethylene (vasp), and 9,10-bis(diphenylphosphino)phenanthrene (dpph) have been prepared and studied by infrared and electronic spectroscopic techniques. The thiocyanate complexes are formulated Pd(vpp)(SCN) 2 Pd(vaa)(SCN) 2 Pd(vasp)(SCN) 2 and Pd(dpph)(NCS)(SCN), and the possible factors promoting the different types of coordination are discussed.

The crystal and molecular stucture of μ-Bis(diphenylarsino)methanehexacarbonyldi-μ-chloro-dirhenium(I)-n-hexane (4/1)

The crystal and molecular structure of the n-hexane solvate of μ- bis(diphenylarsino)methane-hexacarbonyldi-μ-chloro-dirhenium(I), Re2(CO)6(Ph2AsCH2AsPh2)Cl2, has been determined by three-dimensional X-ray diffraction methods. The complex crystallizes in the space group Pī with a 15.763(1), b 19.077(1), c 12.233(1) Ǻ and α 88.745(10), β 110.506(5), γ 92.900(6)�. The structure was solved by conventional Patterson and Fourier methods and refined by a block-diagonal least- squares method to R and Rw of 0.045 and 0.054, respectively, for 7061 independent statistically significant reflections collected by counter methods. The crystal consists of discrete molecules of the complex and n-hexane held together by van der Waals forces. There are two molecules of the dirhenium complex in the crystallographic asymmetric unit with the n-hexane molecule situated about a site of symmetry ī. The binuclear rhenium complex contains bridging halogen atoms and a bridging diarsine ligand. Three carbonyl ligands are also bonded to each rhenium atom, giving the metal atoms approximately octahedral environments. The average Re-As, Re-Cl, and Re-C bond lengths are 2.58, 2.52, and 1.89 Ǻ respectively.