Cyclopentadienylcobalt Complexes Containing Two Phosphine Ligands

The ionic complexes [C₅H₅Co(L)(Ph₂PMe)I]⁺ [I]^- (L = Ph₃P and Ph₂PMe) were prepared by the reactions of cyclopentadienyl(triphenylphosphine)cobalt and cyclopentadienyl(methyldiphenylphosphine)cobalt diiodides with methyldiphenylphosphine. The treatment of these complexes with sodium tetraphenylborate results in the formation of [C₅H₅Co(L)(Ph₂PMe)I]⁺[BPh₄]^- compounds.     

2-Phosphinothioyl- and 2-phosphinoylethylcyclopentadienyl zirconium and titanium complexes. Crystal structure of [η5:η1-C5H4CH2CH2P(O)Ph2]TiCl3

The intracomplex conversion of (2-diphenylphosphanoethyl)cyclopentadienyl zirconium and titanium complexes into the corresponding 2-phosphinothioyl and 2-phosphinoyl derivatives, viz., (η⁵-C₅H₅)[η ⁵-C₅H₄CH₂CH₂P(S)Ph₂]ZrCl₂, [η⁵-C₅H₄CH₂CH₂P(S)Ph₂]ZrCl₃, [η⁵:η¹C₅H₄CH₂CH₂P(O)Ph₂]ZrCl₃·THF, and [η⁵:η ¹-C₅H₄CH₂CH₂P(O)Ph₂]TiCl₃ (7), was performed. The NMR spectroscopy data revealed the following order of the coordination ability of the functional groups with respect to the Zr center: Ph₂P=O > Ph₂P > Ph₂P=S. An analogous order was found for the monodentate ligands (Ph₃P=O > Ph₃P > Ph₃P=S) with respect to (η⁵-C₅H₅)ZrCl₃. The molecular structure of complex 7 was established by X-ray diffraction analysis. Coordination of the Ph₂P=O group to the titanium atom was found retained both in the crystalline state and solution.__________Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 116–122, January, 2005.     

Heterobimetallic complexes of palladium(II) bridged by the mixed phosphine–phosphine oxide ligand Ph2PCH2CH2P(O)Ph2

The mixed phosphine–phosphine oxide Ph₂PCH₂CH₂P(O)Ph₂ (dppeO) reacts with either trans-[PdCl₂(PhCN)₂], Na₂[PdCl₄] or trans-[PdCl₂(DMSO)₂] to give trans-[PdCl₂{¹-Ph₂PCH₂CH₂P(O)Ph₂}₂]. Treatment of the latter with the metal chlorides, MCl₂ · nH₂O (M = Mn, Cu, Co, Zn, Hg; n = 4, 2, 6, 1, 0, respectively) or with Me₂SnCl₂ or SnCl₄ · 5H₂O, or with UO₂(NO₃)₂ · 6H₂O or UO₂(OAc)₂ · 2H₂O gives heterobimetallic complexes: trans-[PdCl₂{-Ph₂PCH₂CH₂P(O)Ph₂}₂MX₂] · nH₂O. The cobalt complex (MX₂ = CoCl₂) was unstable in solution (MeOH or EtOH/CHCl₃), and reverts to trans-[PdCl₂{¹-Ph₂PCH₂CH₂P(O)Ph₂}₂] and CoCl₂. trans-[PdCl₂{¹-Ph₂PCH₂CH₂P(O)Ph₂}₂] does not apparently react with either NiCl₂ · 6H₂O or CdCl₂ · 2.5H₂O.     

Synthese und Charakterisierung von 2‐O‐funktionalisierten Ethylrhodoximen und ‐cobaloximen

Synthesis and Characterization of 2‐O‐Functionalized Ethylrhodoximes and ‐cobaloximes 2‐Hydroxyethylrhodoxime and ‐cobaloxime complexes L—[M]—CH₂CH₂OH (M = Rh, L = PPh₃, 1 ; M = Co, L = py, 2 ; abbr.: L—[M] = [M(dmgH)₂L] (dmgH₂ = dimethylglyoxime, L = axial base) were obtained by reaction of L—[M]^— (prepared by reduction of L—[M]—Cl with NaBH₄ in methanolic KOH) with BrCH₂CH₂OH. H₂O—[Rh]^—, prepared by reduction of H[RhCl₂(dmgH)₂] with NaBH₄ in methanolic KOH, reacted with BrCH₂CH₂OH followed by addition of pyridine yielding py—[Rh]—CH₂CH₂OH ( 3 ). Complexes 1 and 3 were found to react with (Me₃Si)₂NH forming 2‐(trimethylsilyloxy)ethylrhodoximes L—[Rh]—CH₂CH₂OSiMe₃ (L = PPh₃, 4 ; L = py, 5 ). Treatment of complex 1 with acetic anhydride resulted in formation of the 2‐(acet oxy)ethyl complex Ph₃P—[Rh]—CH₂CH₂OAc ( 6 ). All complexes 1 — 6 were isolated in good yields (55—71 %). Their identities were confirmed by NMR spectroscopic investigations ( 1 — 6 : ¹H, ¹³C; 1 , 4 , 6 : ³¹P) and for [Rh(CH₂CH₂OH)(dmgH)₂(PPh₃)]·CHCl₃·1/2H₂O ( 1 ·CHCl₃·1/2H₂O) and py—[Rh]—CH₂CH₂OSiMe₃ ( 5 ) by X‐ray diffraction analyses, too. In both molecules the rhodium atoms are distorted octahedrally coordinated with triphenylphosphine and the organo ligands (CH₂CH₂OH and CH₂CH₂OSiMe₃, respectively) in mutual trans position. Solutions of 1 in dmf decomposed within several weeks yielding a hydroxyrhodoxime complex “Ph₃P—[Rh]—OH”. X‐ray diffraction analysis exhibited that crystals of this complex have the composition [{Rh(dmg)(dmgH) (H₂O)(PPh₃)}₂]·4dmf ( 7 ) consisting of centrosymmetrical dimers. The rhodium atom is distorted octahedrally coordinated. Axial ligands are PPh₃ and H₂O. One of the two dimethylglyoximato ligands is doubly deprotonated. Thus, only one intramolecular O—H···O hydrogen bridge (O···O 2.447(9)Å) is formed in the equatorial plane. The other two oxygen atoms of dmgH^— and dmg^2—, respectively, act as hydrogen acceptors each forming a strong (intermolecular) O···H′—O′ hydrogen bridge to the H′₂O′ ligand of the other molecule (O···O′ 2.58(2)/2.57(2)Å).     

SYNTHESIS AND CHARACTERISATION OF DIORGANOANTIMONY(III) COMPLEXES OF THIOSEMICARBAZONES

Abstract

The interaction of the sodium salts of thiosemicarbazones with diphenylantimony chloride in 1:1 molar ratio in benzene solution lead to the formation of derivatives, Ph₂Sb[SC(NH₂)NN: C(R)R′] where R = H; R′ [dbnd] C₆H₅, CH₃OC₆H₄, C₆H₅CH[dbnd]CH, and R′ [dbnd] CH₃; R′[dbnd]C₆H₅, CH₃OC₆H₄, C₆H₄CH₃, respectively. The resulting complexes have been characterised on the basis of elemental analyses and molecular weight determination. The mode of bonding of the ligands with the metal atom has been proposed on the basis of I.R., ¹H and ¹³C NMR studies. All these ligands are found to behave as monofunctional bidentate moiety in these complexes.     

Ligating properties of tertiary phosphine/arsine sulphides or selenides. Part VII. Synthesis and characterisation of palladium(II) complexes with some mono- and ditertiary phosphine sulphides or selenides

Summary Palladium(II) halides react with triphenylphosphine sulphide or selenide, 1,1-methylenebis(diphenylphosphine sulphide or selenide) (MDPS or MDPSe), 1,3-trimethylene-bis-(diphenylphosphine selenide) (PDPSe) or tetramethyldiphosphine disulphide (TMDPS) forming complexes [PdBr₂ · 2L], [2PdBr₂ · 3L] (L=Ph₃PS or Ph₃PSe), [PdX₂ · L] (X=Cl, L =PDPSe; X=Br, L=MDPS or MDPSe; X=Cl or Br, L=TMDPS) and [3PdBr₂ · 2TMDPS]. Characterisation and stereochemical assignments have been made through elemental analyses, i.r., far i.r. and electronic spectra, magnetic susceptibility and molar conductance data and tga studies. Bidentate ligand complexes have higher thermal stability than the monodentate ligand complexes. Chelation or bridging modes of the bidentate ligands have been demonstrated.     

Trichloro-bridged diruthenium (III,III) complexes: X-ray isomorphous structures of [Ph3X=O···H···O=XPh3][Ru2Cl7(XPh3)2]·0.5(CH2Cl2)(H2O)(X = As or P)

The triply chloro-bridged binuclear complexes [Ph₃X=O···H···O=XPh₃][Ru₂Cl₇(XPh₃)₂]·0.5(CH₂Cl₂)(H₂O) (X = As or P) were obtained from [RuCl₃(XPh₃)₂DMA]·DMA (DMA = dimethylacetamide) CH₂Cl₂/Et₂O solution. The structures were characterized by X-ray diffraction studies. The complexes are formed from two Ru atoms bridged by three chloride anions. The two ruthenium atoms are also coordinated to two non-bridging Cl atoms and an AsPh₃ or PPh₃ ligand respectively. As an interesting feature, the cations of these complexes are protons, trapped in a very short hydrogen bond between two triphenylarsine or triphenylphosphine oxide molecules.     

Crystal and molecular structures of some six‐coordinate tin(IV) halogeno complexes with phosphorus‐containing ligands

Six new complexes of tin(IV) halides with phosphorus‐containing ligands have been fully characterized by single‐crystal X‐ray diffraction at low temperature. Three of the compounds, derived from the diphosphanes bis‐(diphenylphosphino)methane or bis‐(dicyclohexylphosphino)methane, have a novel zwitterionic structure, with five Cl ligands and one unidentate phosphorus‐containing ligand on tin, together with a proton on the second phosphorus atom of the potentially bidentate ligand; these are Cl₅Sn⁻P(Ph₂)CH₂PPh₂H⁺ ( 1 ), Cl₅Sn⁻OP(Ph₂)CH₂‐PPh₂H⁺ ( 2 ), and Cl₅Sn⁻OP(cy₂)CH₂Pcy₂H⁺ ( 3 ). The other three complexes have a bidentate donor attached to the SnX₄ moiety; they comprise Cl₄SnOP(Ph₂)‐(CH₂)₂PPh₂O ( 4 ), a derivative of bis‐(diphenylphosphino)ethane dioxide, I₄SnOP(Ph₂)CH₂PPh₂O ( 5 ), a similar derivative of bis‐(diphenylphosphino)‐methane dioxide, and the very unusual Br₄SnAs‐(Ph₂)(CH₂)₂PPh₂O ( 6 ), with coordination to tin by As and O. Since the starting material for the last compound was Ph₂As(CH₂)₂PPh₂, this result illustrates well the more facile oxidation of P(III) than As(III). © 2009 Wiley Periodicals, Inc. Heteroatom Chem 20:136–143, 2009; Published online in Wiley InterScience ( www.interscience.wiley.com ). DOI 10.1002/hc.20525     

Synthesis of novel heterobimetallic complexes of platinum(II) bridged by the mixed phosphine-phosphine oxide ligands Ph2P(CH2)2P(O)Ph2

Summary The mixed phosphine-phosphine oxides Ph₂P(CH₂)_n-P(O)Ph₂ (n = 1 or 2) react with K₂PtCl₄ to give cis-{PtCl₂- ¹-Ph₂P(CH₂) _n P(O)Ph₂]₂}. Treatment of the latter (n = 2) with transition metal chlorides MCl₂·nH₂O, or with Me₂SnCl₂, SnCl₄·5H₂O, Th(NO₃)₄·xH₂O or UO₂(NO₃)₂· 6H₂O, gives novel heterobimetallic complexes identified as cis-{PtCl₂[-Ph₂P(CH₂)₂P(O)Ph₂]₂MX₂}·nH₂O. Attempts to prepare similar heterobimetallic complexes using the starting complexes {PtX₂[ ¹-Ph₂PCH₂P(O)-Ph₂]₂} (X = C1), cis- or CN, trans-] were unsuccessful. Possible reasons for this are discussed.     

Complex formation of certain neutral sulfur ligands with the lithium ion in tetrahydrofuran

Complex formation of a new group of ligands with the lithium ion has been studied in THF. Stability constants of the [LiL]⁺ complexes have been determined. It was found that the R-S group does not take part in the coordination; the complex-forming capability of the R-S=O group with the lithium ion is no higher than that of Ph₂P=O or (EtO)₂P=O.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 10, pp. 2216–2218, October, 1989.     

Enantiopure Calcium Iminophosphonamide Complexes: Synthesis,Photoluminescence, and Catalysis

The synthesis of calcium complexes ligated by three different chiral iminophosphonamide ligands, L- H ( L =[Ph₂P{N(R)CH(CH₃)Ph}₂]), L′ -H ( L′ =[Ph₂P{NDipp}{N(R)CH(CH₃)Ph}]), (Dipp=2,6-ⁱPr₂C₆H₃), and L′′ -H ( L′′ =[Ph₂P{N(R)CH(CH₃)naph}₂]), (naph=naphthyl) is presented. The resulting structures [ L ₂Ca], [ L′ ₂Ca], and [ L′′ ₂Ca] represent the first examples of enantiopure homoleptic calcium complexes based on this type of ligands. The calcium complexes show blue–green photoluminescence (PL) in the solid state, which is especially bright at low temperatures. Whereas the emission of [ L′′ ₂Ca] is assigned to the fluorescence of naphthyl groups, the PL of [ L ₂Ca] and [ L′ ₂Ca] is contributed by long-lived phosphorescence and thermally activated delayed fluorescence (TADF), with a strong variation of the PL lifetimes over the temperature range of 5–295 K. Furthermore, an excellent catalytic activity was found for these complexes in hydroboration of ketones at room temperature, although no enantioselectivity was achieved.     

Synthesis of crown ether complexes of alkali-metallated organophosphine oxides and insertion reactions with isonitriles

The synthesis and crystal structures of the alkali-metallated organophosphine oxides [{Ph₂P(O)CH₂}K · 18-crown-6] (1) and [{Ph₂P(O)CH₂}Na · 15-crown-5] (2) are reported. In addition the insertion reaction of an isonitrile into the C-Li bond of [{Ph₂P(O)CH₂}Li] is reported and the crystal structure of the resulting tetrameric complex [Ph₂P(O)CHCHN(Cy)Li]₄ (3) (Cy = Cyclohexyl) described.     

Structural,Theoretical, and Spectroscopic Study of Mercury(II) Complexes of two New Unsymmetric Phosphorus Ylides

Abstract

The reaction of Ph₂PCH₂PPh₂ (dppm) with 4-methylphenacyl bromide and 2-(bromoacetyl)naphthalene in chloroform produce the new phosphonium salts [Ph₂PCH₂PPh₂CH₂C(O)C₆H₄Me]Br (1) and [Ph₂PCH₂PPh₂CH₂C(O)C₁₀H₇]Br (2). Further, by reaction of the monophosphonium salts of dppm with the strong base Et₃N the corresponding bidentate phosphorus ylides, Ph₂PCH₂P(Ph)₂ = C(H)C(O)C₆H₄Me (3) and Ph₂PCH₂P(Ph)₂ = C(H)C(O)C₁₀H₇ (4) were obtained. The reaction of these ligands with mercury(II) halides in dry methanol led to the formation of the mononuclear complexes {HgX ₂[(Ph₂PCH₂PPh₂C(H)C(O)C₆H₄Me)]} [X = Cl (5), Br (6), and I (7)] and {HgX ₂[(Ph₂PCH₂PPh₂C(H)C(O)C₁₀H₇)]} [X = Cl (8), Br (9), and I (10)]. Characterization of the obtained compounds was performed by elemental analysis, IR, ¹H, ³¹P, and ¹³C NMR spectra. The structure of compounds 3 and 10 are unequivocally determined by single crystal X-ray diffraction techniques. X-ray analysis of 10 reveals the presence of mononuclear complex containing Hg atom in a distorted tetrahedral environment. In all complexes, the title ylides are coordinated through the ylidic carbon and the phosphine phosphorus. Computational studies on ligand 4 and complexes 8, 9, and 10 at DFT (B3LYP) level of theory are also reported. It was shown that the formation of P,C-coordinated 1+1 complex 10 is energetically more favored than corresponding P,P-coordinated 1+2 product.

[Supplemental materials are available for this article. Go to the publisher's online edition of Phosphorus, Sulfur, and Silicon and the Related Elements to view the following free supplemental files: Additional figures]     

Spectral and crystallography studies of new palladacycle complexes with P,C‐ and C,C‐donor ligands; Application of (OAL16) to optimizing the yield of Mizoroki‐Heck reaction

The new symmetrical diphosphonium salt [Ph₂P(CH₂)₂PPh₂(CH₂C(O)C₆H₄Br)₂] Br₂ ( S ) was synthesized in the reaction of 1,2‐bis (diphenylphosphino) ethane (dppe) and related ketone. Further treatment with NEt₃ gave the symmetrical α‐keto stabilized diphosphine ylide [Ph₂P(CH₂)₂PPh₂(CHC(O)C₆H₄Br)₂] ( Y ¹ ). The unsymmetrical α‐keto stabilized diphosphine ylide [Ph₂P(CH₂)₂PPh₂(CHC(O)C₆H₄Br)] ( Y ² ) was synthesized in the reaction of diphosphine in 1:1 ratio with 2.3′‐dibromoacetophenone, then treatment with NEt_3. The reaction of dibromo (1,5‐cyclooctadiene)palladium (II), [PdBr₂(COD)] with this ligand ( Y ¹ ) in equimolar ratio gave the new C,C‐chelated [PdBr₂(Ph₂P(CH₂)₂PPh₂(C(H)C(O)C₆H₄Br)₂)] ( 1 ) and with unsymmetrical phosphorus ylide [Ph₂P(CH₂)₂PPh₂C(H)C(O)C₆H₄Br] ( Y ² ) gave the new P, C‐chelated palladacycle complex [PdBr₂(Ph₂P(CH₂)₂PPh₂C(H)C(O)Br)] ( 2 ). These compounds were characterized successfully by FT‐IR, NMR (¹H, ¹³C and ³¹P) spectroscopic methods and the crystal structure of Y ¹ and 2 were elucidated by single crystal X‐ray diffraction. The results indicated that the complex 1 was C, C‐chelated whereas complex 2 was P, C‐chelated. These air/moisture stable complexes were employed as efficient catalysts for the Mizoroki‐Heck cross‐coupling reaction of several aryl chlorides, and the Taguchi method was used to optimize the yield of Mizoroki‐Heck coupling. The optimum condition was found to be as followed: base; K₂CO₃, solvent; DMF and loading of catalyst; 0.005 mmol.     

Complex Formation of Potassium Hexachloroplatinate with 18-Crown-6 and Dibenzo-18-Crown-6 in Acetonitrile

The products of the reactions between potassium hexachloroplatinate {K₂PtCl₆} and 18-crown-6 or dibenzo-18-crown-6 in acetonitrile were studied. Pure crystalline compounds [2K·2(18-crown-6)· 2CH₃CN]²⁺·[PtCl₆]^2-·2H₂O, [2K·dibenzo-18-crown-6·CH₃CN]^{2 +}·[PtCl₆]^{2 -}, and [2K·dibenzo-18-crown-6·CH₃CN]^{2 +}·[Pt₂Cl₁₀]^{2 -} were obtained. Physicochemical properties of these compounds were studied, and their near- and far-IR IR spectra and thermogravimetric curves were considered. The composition of the complexes is determined by metal:ligand molar ratio and crown ether nature. It was found that acetonitrile is coordinated via the nitrogen atom.     

Synthesis,complexing properties,and selectivity of bis(diphenylphosphorylmethyl) ethers of oligoethylene glycols. Crystal structure of 1,3-bis(diphenylphosphoryl)-2-oxapropane

A convenient method of synthesis of phosphoryl-substituted podands with dipehnylphosphorylmethyl end groups of the general formula Ph₂P(O)CH₂O(CH₂CH₂O)_nCH₂P(O)Ph₂ (Lⁿ, n = 0–6) is described. The stability constants of the complexes of the podands with alkali metal 2,4-dinitrophenolates were determined by conductometry. The ion-selective properties of the podands with respect to alkali and alkaline-earth metal cations were assessed by ionometry. The crystal structure of 1,3-bis(diphenylphosphoryl)-2-oxapropane was established by X-ray diffraction analysis.     

Gallium(III) halide complexes with phosphines,arsines and phosphine oxides – a comparative study

The phosphine oxide complexes [GaX₃(Me₃PO)] and [(GaX₃)₂{μ-o-C₆H₄(CH₂P(O)Ph₂)₂}] have been prepared and characterised by microanalysis, IR and multinuclear NMR (¹H, ¹³C{¹H}, ³¹P{¹H} and ⁷¹Ga) spectroscopy. The structures of [GaCl₃(Me₃PO)], [(GaBr₃)₂{μ-o-C₆H₄(CH₂P(O)Ph₂)₂}] and of the ionic product [GaI₂(Me₃PO)₂][GaI₄] have been determined and show that the Lewis acidity of the gallium halides towards phosphinoyl ligands diminishes as the halogen becomes heavier. The [GaX₃(Ph₃E)] (X = Cl, Br or I; E = P or As) and [(GaX₃)₂{μ-o-C₆H₄(CH₂PPh₂)₂}] (X = Br or I) have been prepared and their structural and spectroscopic properties compared with those of the phosphinoyl complexes. The results, and competitive solution NMR studies, show that Ga(III) binds the hard R₃PO in preference to the softer phosphine or arsine ligands. Hydrolysis of gallium(III) phosphines is shown to lead to [R₃PH][GaX₄], but in contrast to some other p-block halides, GaX₃ do not promote air-oxidation of R₃P to R₃PO.     

Cyclic acyl complexes of palladium(II). Synthesis and NMR spectroscopy of acyl complexes derived from quinoline-8-carbaldehyde and 2-(dimethylamino)benzaldehyde

The room temperature syntheses of new chelating acyl palladium(II) complexes, [Pd(μ-Cl)(C(O)C₉H₆N)]₂ and [Pd(μ-Cl)(C(O)C₆H₄N(CH₃)₂]₂, derived from quinoline-8-carbaldehyde and 2-(dimethylamino)banzaldehyde are described. These chloro bridged dimers may be cleaved with neutral phosphine and nitrogen ligands, L, to give the monomeric [PdCl(C(O)C₉H₆N)L] and [PdCl(C(O)C₆H₄N(CH₃)₂)L] compounds. ¹H-, ¹³C- and ³¹P-NMR data for the new complexes are reported.     

Synthesis and structure of bismuth-containing complexes [(Ph4BiO)2{2,5-(CH3)2C6H3S(O)}] 2 + [Ph2Bi2I6]2−,[(Ph4Bi]+[PhBi(C5H5N)I3]−, [Ph4Sb] 4 + [Bi4I16]4−⋅2(CH3)2 C=O, and [Ph4Sb] 3 + [Bi5I18]3−

The reactions of tetraphenylbismuthonium and -stibonium salts Ph₄EX (E = Bi, Sb; X = I, OSO₂ (C₆H₃(CH₃)₂-2,5), OSO₂C₆H₃(OH-4)(COOH-3)) with bismuth triiodide in acetone afford complexes [Ph₄Bi]⁺[PhBi(C₅H₅N)I₃]^-, [(Ph₄BiO)₂S(O){2,5-(CH₃)₂C₆H₃S(O)} [Ph₂Bi₂I₆]^2–, [Ph₄Sb [Bi₄I₁₆]^4-·2(CH₃)²C=O, and [Ph₄Sb] ₃₊ ⁺ [Bi₅I₁₈]^3-, whose structural units, according to the X-ray diffraction data, are tetraphenylbismuthonium (-stibonium) cations and mono-, di-, tetra-, and pentanuclear anions, respectively.     

Mixed ligand transition metal complexes of tertiary phosphines and 5-phenyl-l,3,4-oxadiazole-2-thione

Transition metal complexes containing two types of ligands: 5-phenyl-1,3,4-oxadiazole-2-thione ion (L) and tertiary phosphines, have been prepared. The complexes, [ML₂A₂] [M = Pd or Pt; A = PPh₃ or Ph₂PCH₂CH₂P(O)Ph₂] and [ML₂B] (M = Co, Ni, Pd or Pt; B = Ph₂PCH₂PPh₂ or Ph₂PCH₂CH₂PPh₂), were characterized by elemental analysis, molar conductance, i.r., u.v.–vis., ³¹P-n.m.r., magnetic susceptibility measurements and mass spectra.