Transition-Metal Complexes with Bidentate Ligands Spanning trans-Positions. IX. Preparation and 1H-NMR. Studies of complexes [MX2(1)] and [M′Cl(CO)(1)] (M = Pd,Pt; M′ = Rh,Ir; X = Cl,Br, I; 1 = 2, 11-Bis-(diphenylarsinomethyl)benzo[c]phenanthrene) and crystal and molecular structure of [PtCl2(1)]

The preparation of the bidentate ligand 2, 11-bis(diphenylarsinomethyl)benzo-[c]-phenanthrene ( 1 ) is described. This ligand reacts with appropriate substrates to give mononuclear square planar complexes of type [MX₂( 1 )] (M = Pd, Pt; X = Cl, Br, I) and [M′Cl(CO)( 1 )] (M′ = Rh, Ir) in which ligand 1 spans trans-positions. This is confirmed by the crystal structure of [PtCl₂( 1 )]. ¹H-NMR. spectra of the complexes are discussed and compared with those of model compounds trans-[MCl₂( 12 )₂] (M = Pd, Pt) and [M'Cl(CO)( 12 )₂] (M′ = Rh, Ir; 12 = AsBzPh₂).     

1,3-diaryltriazenido complexes of ruthenium(I), (II) and (III), and of osmium(III), rhodium(III) and iridium(III)

The synthesis and characterization of the platinum metal—1,3-diaryltriazenido complexes [Ru(ArNNNAr)(CO)₃]₂, [Ru(ArNNNAr)₂]₂, cis-Ru(ArNNNAr)₂(CO)₂, MX₂(ArNNNAr)(PPh₃)₂ (M = Ru, Os; X = Cl, Br) and M′(ArNNNAr)₃ (M′= Ru, Os, Rh and Ir) are reported. Axial ligand substitution in [Ru(ArNNNAr)(CO)₃]₂ and adduct formation by [Ru(ArNNNAr)₂]₂ are described. In contrast to other known Ru(II)/Ru(II) “lantern” molecules, the species [Ru(ArNNNAr)₂]₂ have measured magnetic moments equivalent to ca one unpaired electron per dimer, which are presumably due to population of the spin states σ²π⁴δ²π^*4 and σ²π⁴δ²π^*3σ^*1.     

Mononuclear and binuclear lanthanum(III) complexes of macrocyclic ligands derived from 2,6-diacetylpyridine

Two novel series of complexes of types [La(DAPCH)X₂]X and [La(DAPTC)X₂]X (DAPCH = a potentially pentadentate ligand derived from 2,6-diacetylpyridine and carbohydrazide; DAPTC = a potentially tridentate ligand derived from 2,6-diacetylpyridine and thiocarbohydrazide; X = Cl, Br or NO₃) have been synthesized and characterized by elemental analyses, conductance measurements and IR spectral data. All these complexes contain terminal hydrazinic nitrogen atoms with an unshared electron pair and may take part in nucleophilic condensations. Therefore, the reactions of these complexes with 2,6-diacetylpyridine have also been studied which cause ring closure and formation of macrocyclic ligand complexes. Two types of cyclic products, viz. mononuclear [La(mac)X₂]X, [La(mac′)X₂]X and binuclear [La₂(mac)X₄]X₂, [La₂(mac′)X₄]X₂ (mac- = macrocyclic ligand derived from DAPCH and 2,6-diacetylpyridine; mac′ = macrocyclic ligand derived from DAPTC and 2,6-diacetylpyridine; X = Cl, Br or NO₃) have been isolated by carrying out the reactions by different methods. The IR spectra of these cyclic products are reported.     

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.     

Darstellung und spektroskopische Charakterisierung der Nona-halogenodiiridate(III), [Ir2X9]3−, X = Cl,Br

Preparation and Spectroscopic Characterization of Nonahalogenodiiridates(III), [Ir₂X₉]^3?, X = Cl, Br The pure nonahalogenodiiridates(III), A₃[Ir₂X₉] (A = K, Cs, tetraalkylammonium; X = Cl, Br) have been prepared. They are formed from the monomer hexahalogenoiridates(III) which are bridged to confacial bioctahedral complexes by ligand abstraction in less polar organic solvents. The IR and Raman spectra exhibit bands in three characteristic regions; at high wavenumbers stretching vibrations with terminal ligands ν(Ir?Cl_t): 360?300, ν(Ir?Br_t): 250?220; in a middle region with bridging ligands ν(Ir?Cl_b): 290?235, ν(Ir?Br_b): 205?190 cm^?1; the deformation bands are observed at distinct lower frequencies. The distance between ν(Ir?X_t) and ν(Ir?X_b) increases with decreasing size of the cations. The electronic spectra measured at thin films of the pure complex salts at 10 K show some intensive charge transfer transitions in the UV and one or two weak d? d bands in the visible region.     

Ruthenium(III)-Phthalocyanine: Darstelllung und Eigenschaften von Di(halogeno)phthalocyaninato(1−)ruthenium(III), [Ru(X)2Pc] (X = Cl,Br, I)

Ruthenium(III) Phthalocyanines: Synthesis and Properties of Di(halo)phthalocyaninato(1?)ruthenium(III) Di(halo)phthalocyaninato(1?)ruthenium(III), [Ru(X)₂Pc^?] (X = Cl, Br, I) is prepared by oxidation of [Ru(X)₂Pc^2?]^? (Cl, Br, OH) with halogene in dichloromethane. The magnetic moment of [Ru(X)₂Pc^?] is 2,48 μ_B (X = Cl) resp. 2,56 μ_B (X = Br) in accordance with a systeme of two independent spins (low spin Ru^III and Pc^?: S = 1/2). The optical spectra of the red violet solution of [Ru(X)₂Pc^?] (Cl, Br) are typical for the Pc^? ligand with the “B” at 13.5 kK, “Q₁” at 19.3 kK and “Q₂ region” at 31.9 kK. Sytematic spectral changes within the iron group are discussed. The presence of the Pc^? ligand is confirmed by the vibrational spectra, too. Characteristic are the metal dependent bands in the m.i.r. spectra at 1 352 and 1 458 cm^?1 and the strong Raman line at 1 600 cm^?1. The antisymmetric Ru? X stretch (v_as(Ru? X)) is observed at 189 cm^?1 (X = I) resp. 234 cm^?1 (X = Br). There are two interdependent bands at 295 and 327 cm^?1 in the region expected for v_as(Ru? Cl) attributed to strong interaction of v_as(Ru? Cl) with an out-of-plane Pc^? tilting mode of the same irreducible representation. Only the symmetric Ru? Br stretch at 183 cm^?1 is selectively enhanced in the resonance-Raman(RR) spectra. The Raman line at 168 cm^?1 of the diiodo complex is assigned to loosely bound iodine. The broad band at 978 cm^?1 in the RR spectra of the dichloro complex is due to an intraconfigurational transition within the electronic ground state of low spin Ru^III split by spin orbit coupling.     

Double complex salts [M(NH3)5Cl][M′Br4] (M = Rh, Ir, Co, Cr, Ru; M′ = Pt, Pd): Synthesis, x-ray diffraction characterization, and thermal properties

Double complex salts (DCSs) with [M(NH₃)₅Cl]²⁺ (M = Rh, Ir, Co, Cr, Ru) cations and [PtBr₄]^2? anions were prepared in high yields. The salts were two-phase mixtures of the anhydrous and monohydro DCSs. Anhydrous analogues containing [PdBr₄]^2? anions with M = Cr or Ru were synthesized. All the compounds were characterized using a set of physicochemical methods. The crystal structure of chloropentaamminechromium(III) tetrabromopalladate(II) was solved: space group Pnma, Z = 4, a = 17.068(2) Å, b = 8.315(12) Å, c = 9.653(14) Å. The [M(NH₃)₅Cl][M′X₄] (M = Rh, Ir, Co, Cr, Ru; M′ = Pd, Pt; X = Cl, Br) compounds were shown to be isostructural. The [M(NH₃)₅Cl][PtBr₄] · H₂O monohydrates are isostructural to the [M(NH₃)₅Cl][PdCl₄] · H₂O monohydrates (space group P2₁/c, z = 4). The properties of the compounds were comparatively analyzed. The tendencies of the thermal stability of the complexes were elucidated. The thermolysis products of the double complex salts obtained under a helium or hydrogen atmosphere were studied.     

Some transition metal complexes of new terdentate ligands: Bis[2-(diphenylphosphino)ethyl]benzylamine and bis[2-(diphenylarsino)ethyl)benzylamine

Complexes of the terdentate ligands bis[2-diphenylphosphino)ethyl]benzylamine (DPBA) and bis[2-(diphenylarsino)ethyl]benzylamine (DABA) with Co(II), Ni(II), Pd(II), Pt(II), Rh(III), Ir(III), Rh(I) and Ir(I) are reported. The ligand DPBA reacts with Co(II) ion to form two types of complexes: a high-spin, paramagnetic, tetrahedral Co(II) complex of composition [CoCl(DPBA)]Cl and a low-spin, paramagnetic, square-planar complex of composition [CoBr(DPBA)]B(C₆H₅)₄. The reaction of DPBA with Ni(II) ion in methanol yields low-spin, diamagnetic, square-planar complexes of type [NiX(DPBA)]Y [X = Cl, Br or I; Y = Cl or B(C₆H₅)₄]. Four-coordinate, square-planar, cationic complexes of type [MY(L⁺[M = Pd(II), Pt(II), Rh(I) or Ir(I); Y = Cl or P(C₆H₅)₃; L = DPBA or DABA], were obtained on reaction of L with various starting materials containing these metal ions. Reaction of DPBA and DABA with rhodium and iridium trichlorides gave octahedral, neutral complexes of general formula [MCl₃(L)] (M = Rh or Ir, L = DPBA or DABA). All the complexes were characterized on the basis of their elemental analysis, molarconductance data, magnetic susceptibilities, electronic spectra, IR spectral measurements, and¹H and³¹P-{¹H} NMR spectral data.     

Metal Complexes of Aniline: Infrared and Raman Spectra

Abstract

The literature for the years 1965–1987 has been searched for all significant papers which refer to the vibrational spectra of metal complexes of aniline and substituted anilines. These papers have been reviewed with particular reference to isotopic labelling and metal ion substitution studies as assignment techniques and to the structural and bonding information which can be derived from the spectra. Compounds of the following classes are included: [M(an)₂X₂] (M = Mn, Co, Ni, Cu, Zn, Cd, Hg; an = aniline, X - Cl, Br, I, NCS); cis- and trans-[Pt(an)₂X₂] (X = Cl, Br, I, NO₂); [M(R-an)₂X₂] (M = Mn, Co, Ni, Cu, Zn; R-an = o-, m- and p-toluidine and other substituted anilines; X = Cl, Br, I); aniline adducts of metal β-ketoenolates; the complexes trans-[PtL(R-an)X₂] (L = CH₂?CH₂ or CO, R-an = aniline or a substtuted aniline, X = Cl, Br); and other miscellaneous systems comprising aniline as a ligand.     

Palladium(II)-, Platin(II)-, Ruthenium(II)-, Rhodium(III)- und Iridium(III)-Komplexe von Desoxyfructosazin

Metal Complexes of Biologically Important Ligands. CIII. [1] Palladium(II), Platinum(II), Ruthenium(II), Rhodium(III), and Iridium(III) Complexes of Desoxyfructosazine The reactions of the pyrazine derivative desoxyfructosazin(pz) with K₂PtCl₄ and with the chlorobridged [M(PR₃)Cl₂]₂ (M = Pd, Pt), [(η⁵-C₅Me₅)MCl₂]₂ and [(η⁶-p-Cymol)RuCl₂]₂ give the watersoluble complexes cis-Cl₂Pt(pz)₂, (R₃P)(Cl)M(pz)M(Cl)(PR₃) (M = Pd, Pt), (η⁵-C₅Me₅)(Cl)₂M(pz)M(Cl)₂(η⁵-C₅Me₅) (M = Rh, Ir), (η⁶-p-Cymol)(Cl₂)Ru(pz)Ru(Cl)₂(η⁶-p-Cymol).     

Co-ordination compounds of diacetyldihydrazone and diacetylbis(monomethylhydrazone)

Summary Diacetyldihydrazone (DADH) forms only six-coordinate complexes with iron(II), cobalt(II), nickel(II) and zinc(II). In M(DADH)₂X₂ (M=Fe, X=Br or I; M=Co, X=I; M=Ni, X=Cl, Br or NCS) the ligand is chelating in the [M(DADH)₃]²⁺ cations, while in M(DADH)₂X₂ (M=Co, X=Cl or Br; M=Ni, X=Cl or Br) the ligand is probably bridging and bidentate. Diacetylbismonomethylhydrazone (DAMH), by contrast, forms predominantly tetrahedral complexes M(DAMH)X₂ (M=Fe or Co, X=Cl or Br; M=Ni, X=Br; M=Co, X=NCS; M=Zn, X=Cl, Br or NCS) and some octahedral complexes M(DAMH)₂X₂ (M=Co, X=NCS; M=Ni, X=Br). The i.r. spectra, electronic spectra and magnetic moments of the complexes are discussed.     

Mixed ligand complexes of ruthenium(III), rhodium(III) and iridium(III) with dipicolinic acid and some monobasic bidentate nitrogen,oxygen donor ligands

The trivalent ruthenium, rhodium and iridium complexes of dipicolinic acid and its mixed ligand complexes with several nitrogen, oxygen donor molecules, of types: Na[M(dipic)₂]·2H₂O and [M(dipic)(N-O)]·nH₂O (where M = Ru(III), Rh(III) or Ir(III); dipicH₂ = dipicolinic acid; NOH represents different nitrogen, oxygen donor molecules, viz., picolinic acid, nicotinic acid, isonicotinic acid, glycine, aminophenol, o- or p-aminobenzoic acid), have been synthesized and characterised on the basis of elemental analyses, electrical conductance, magnetic susceptibility measurements and spectral (electronic and infrared) data. The parent dipicolinic acid complexes are found to have a six-coordinate pseudooctahedral structure, whereas for mixed ligand complexes, a polymeric six-coordinate structure has been assigned. Various ligand field and nephelauxetic parameters have also been evaluated.     

Antimony(III) and bismuth(III) halide complexes of 2-methyl-benzoxazole

In the antimony(III) and bismuth(III) complexes of 2-methyl-benzoxazole: SbX₃·L (X = Cl, Br), SbI₃·2.5L, MX₃·L·H₂O (M = Sb, X = I; M = Bi, X = Cl, Br), SbCl₄·HL, SbBr₅·2HL, BiCl₅·2HL. Bi₂X₉·3HL (X = Br, I) the ligand is O-bonded to the metal.     

Crystal Structure of [M(NH3)5Cl]2[IrCl6]Cl2 (M = Co, Rh, Ir) Binary Complex Salts

Binary complex salts of M(NH₃)₅Cl]₂[IrCl₆]Cl₂ composition, where M = Co(III), Rh(III), or Ir(III), have been studied. All phases are isostructural with [M(NH₃)₅Cl]₂[PtCl₆]Cl₂ complexes [M = Rh(III) and Ir(III)]; Xray structural and crystallochemical analysis have been performed.     

Isolation of [Rh(diolefin)X2]- species and their reactions with P- or N-donor ligands,tin(II) halides and carbon monoxide

Anionic [Rh(diolefin)X₂]⁻ species (X = Cl, Br) have been prepared and their reactions studied. The reactions with monodentate ligands led to neutral tetracoordinated complexes, and with N-donor bidentate ligands (Rh : LL = 2 : 1) gave Rh(X)(diolefin)(LL), [Rh(diolefin)(LL)]⁺[Rh(diolefin)X₂]⁻, or [Rh(diolefin)(LL)]X compounds, depending on the nature of LL or X. Reactions with carbon monoxide involved diolefin displacement. A trichlorostannato complex was obtained from the [Rh(COD)Cl₂]⁻ species. Reactions of [Rh(COD)Br]₂ with bidentate N-donor ligands were also studied.     

Mixed dimethyl sulfoxide-thiocarbamic ester complexes of platinum(II) halides

Summary The platinum(II) halidecis-[Pt(DMTC)(DMSO)X₂] andcis-[Pt(DETC)(DMSO)X₂](X=Cl or Br; DMSO=dimethyl sulfoxide; DMTC=EtOSCN-Me₂; DETC=EtOSCNEt₂) adducts and the platinum(II) and palladium(II) halide adducts,trans-[M(DETC)₂X₂] (M=Pt or Pd; X=Cl or Br), have been prepared. The complexes were characterized by i.r., and¹H and¹³Cn.m.r. spectroscopy. Both DMTC and DETC coordinate through the sulphur atoms. The 1:2 DETC complexes present the usualtrans configuration, whereas the presence of DMSO favourscis geometry in the mixed species.     

Carbonyl complexes of rhodium(I) and rhodium(III) with 2,2′-biquinoline

Novel carbonyl complexes of rhodium(I) and rhodium(III) containing the bidenate nitrogen donor ligand 2,2′-biquinoline (biq) have been prepared; they are of the types RhX(CO)₂ biq and RhX(CO)biq (X = Cl, Br, I). Cationic carbonyl and substituted carbonyl complexes of the types [Rh(CO)₂biq]ClO₄ and [Rh(CO)biqL₂]ClO₄, where L is tertiary phosphine or arsine have also been isolated. In spite of considerable steric crowding around the nitrogen atoms, 2,2′-biquinoline behaves much like 2,2′-bipyridine in forming carbonyl complexes of rhodium.     

Adducts of coordination compounds-XIII. Nitrates,hydrogen and silver dinitrates,and polysilver nitrates of trans-dihalotetrakispyridinerhodium(III) and iridium(III) ions

The synthesis and characterization, chiefly as salts of the anions [X(ONO₂)₂]⁻ (X = H⁺ or Ag⁺) (by analysis, X-ray powder photography, vibrational spectra and thermogravimetry) of adducts of the nitrates trans-[M(L)₄X₂](NO₃) (M =Rh or Ir; L = pyridine, perdeuteriopyridine or 4-methylpyridine; X = Cl or Br) with hydrogen nitrate and silver nitrate are described.     

Nickel(II)- und Kobalt(II)-Komplexe des trans-2-Äthylmercapto-cyclohexyl-phenylphosphins

Preparation and properties of nickel(II) and cobalt(II) chelates of the bidentate ligand trans-2-ethylthio-cyclohexyl-phenylphosphine (ÄMCPP) are described. Three types of nickel(II) complexes have been obtained from ÄMCPP: the four-coordinated, square planar [Ni(ÄMCPP)₂]X₂ (X = J, Br, ClO₄); five-coordinated [Ni(ÄMCPP)₂X]X (X = Cl, NCS), [Ni(ÄMCPP)₂X]BPh₄ (X = Cl, NCS) and the octahedral [Ni(ÄMCPP)₂Cl₂]. Cobalt(II) forms tetrahedral 1.1-[Co(ÄMCPP)X₂] (X = Br, Cl) and 1.2-Co(ÄMCPP)₂X₂(X = Br, Cl, NCS) complexes. All compounds were characterized by electronic reflectance and absorption spectra, conductivity and magnetic measurements.     

Synthesis and characterization of 1-Methyl-4-mercaptopiperidine complexes of nickel(II), palladium(II) and platinum(II)

Summary Complexes of formulae Ni(HRS)₂X₂ (X=Cl or Br), M(HRS)₂Y₂ (M=Ni or Pd; Y=NO₂ or C1O₄), Pd(HRS)X₂ (X=Cl, Br or I), Pt(HRS)X₂ (X=Cl or Br), Pt(HRS)₂(ClO₄)₂ and M(RS)₂ (M=Pd or Pt) where HRS and RS denote 1-methyl-4-mercaptopiperidine in the zwitterionic or in the thiolato form, respectively, have been prepared and characterized. In all the complexes the ligands are coordinated exclusively through sulphur. Polymeric structures consisting of square-planar geometry with sulphur-bridged metal atoms are proposed in each case.