Tetraazaadamantane derivatives of group VI metal carbonyls

Summary Tetraazaadamantane (taad) reacts with group VI metal hexacarbonyls to give mononuclear (taad)M(CO)₅ (M=Cr, Mo and W) derivatives. Mixed ligand metal tricarbonyls,cis- (L-L)(taad)M(CO)₃ (L-L=o-phenanthroline or 2,2-bipyridine; M=Cr and Mo) have also been synthesised. Bromine or iodine reacts with (taad)M(CO)₅ (M=Cr and Mo) to give [(taad)M(CO)₅X]⁺X^– (X=Br or I). Nitrosyl chloride reacts with (taad)M(CO)₅ at room temperature to yieldmer- (taad)M(CO)₃NOCl while with the mixed (L-L)(taad)-Mo(CO)₃ complex, a mixture of (L-L)Mo(NO)₂Cl₂ and (L-L)Mo(CO)₂NOCl was obtained. An analogous reaction with (L-L)(taad)Cr(CO)₃, gave only (L-L)Cr(NO)₂Cl₂ derivatives. The products have been characterised by elemental analysis, i.r. spectra, conductivity data and magnetic measurements.     

Compounds of imidazoles with ruthenium(III) chloride

Summary Reaction of ruthenium(III) chloride with imidazole(Im) and different substituted imidazoles,viz. N-methylimidazole (N-MeIm), 2-methylimidazole(2-MeIm), 4-methylimidazole (4-MeIm),N-vinylimidazole(N-VIm), 2-methyl- 1-vinyl-imidazole(2-Me-1-VIm), 1,2-dimethylimidazole(1,2-Me,Im), 2-ethylimidazole(2-EtIm) and 2-ethyl-4(5)-methylimidazole (2-Et-4(5)-MeIm] yield products of the types [Ru₂L₄Cl₆] · 2 H₂O (L = N-VIm or 4-MeIm), [Ru₂L₄Cl₆] · 4 H₂O (L = Im or 2-Et-4(5)-MeIm), [Ru₂L ³ (H₂O)Cl₆] (L =N-MeIm or 2-MeIm), [Ru₂L ² (H₂O)₂Cl₆] (L = 1,2-Me₂Im or 4-MeIm), [Ru(2-Me-1-VIm)₃Cl₃] · H₂O and [Ru(2-EtIm)₃(H₂O)Cl₂]. These compounds were characterised by elemental analyses, conductometric measurements, i.r. and electronic spectral analyses. Magnetic moments range from 1.01 to 1.9 B.M. The e.s.r. spectra and g values of some of the compounds are indicative of high distortion.     

Complexes of palladium,platinum and rhodium with 2,2′-biquinoline and 2-(2′-pyridyl)quinoline

Summary The reactions of 2,2-biquinoline(biq) with M(PhCN)₂X₂ (M=Pd; X=Cl or Br; M=Pt, X=Cl, Br or I), K₂PtCl₄ and RhCl₃·3H₂O and of 2-(2-pyridyl)quinoline (pq) with K₂PtCl₄ and RhCl₃·3H₂O have been investigated. The isolated complexescis-[Pd(biq)X₂] (X=Cl or Br),cis-[Pt(biq)Cl₂],cis-[Pt(biq)Cl₂]·H₂O,trans-[Pt(biq)₂Br₂]·5H₂O, [Pt₃(biq)₂I₆],mer-[Rh(biq)Cl₃-(H₂O)] andmer-[Rh(pq)Cl₃(H₂O)] have been characterized by elemental analyses, conductivity measurements, i.r., electronic, and¹H n.m.r. spectra. The reaction of pq with K₂PtCl₄ in 1M H₂SO₄ gave the salt 2-(2-pyridyl) quinolinium tetrachloroplatinate(II) pentahydrate, (pqH)₂[PtCl₄]·5H₂O; when the reaction was carried out in aqueous acetone,cis-[Pt(pq)Cl₂] was obtained. A new method for the synthesis ofcis-[Rh(biq)₂X₂]X (X=Cl or Br) is described; both compounds have been further characterized by¹H n.m.r.     

Divalent 3d metal chloride adducts with 2′-deoxyadenosine

Summary Adducts of 2-deoxyadenosine (dado) with chlorides of dipositive 3d metal ions (M=Mn, Fe, Co, Ni, Cu and Zn) were prepared by boiling, under reflux, mixtures of ligand and the metal salt in HC(OEt)₃·EtOH. The solid complexes isolated are either 21 or 11 adducts of dado and metal chloride,i.e.: M(dado)₂Cl₂ (M=Co or Cu), M(dado)₂Cl₂·2H₂O (M=Mn or Zn), Fe(dado)Cl₂ and Ni(dado)Cl₂·2H₂O. The 21 adducts are monomeric distorted tetrahedral (M=Co or Cu) or hexacoordinated (M=Mn or Zn). The 11 complexes are apparently single-bridged linear polymeric species, involving a [M-(dado)]_x backbone (M=Fe or Ni), two terminal Cl- and for M=Ni, two aqua ligands. Terminal dado is most probably N(7)-bound, while bidentate bridging dado bindsvia N(1), N(7).Presented in part at the XXVIII ICCC, see ref. 1.     

Synthesis and polymerization studies of several chloro and cyano epoxides

The polar epoxides, glycidonitrile, dimethyl glycidonitrile, tetracyanoethylene oxide, epicyanohydrin, 4,4,4-trichlorobutylene-1,2-epoxide, and 1,1-dichloro-3,4-epoxy-1-butene were prepared, characterized by their infrared and nuclear magnetic resonance spectra and their polymerizations studied. Epicyanophydrin was found to be an unpolymerizable dimer, and those epoxides with a cyano group attached directly to the epoxide ring could not be polymerized. The halogenated epoxides, 4,4,4-trichlorobutylene-1,2-epoxide and its dehydrochlorination product, 1,1-dichloro-3,4-epoxy-1-butene were polymerized to high polymers with a complex catalyst from aluminum alkyl, acetyl acetone, and water. The polymerization of these monomers gave low conversions and required large amounts of catalyst. Higher conversions were obtained by copolymerization with propylene oxide or terpolymerization with propylene oxide and allyl glycidyl ether. The polymerizability of the substituted epoxide in (where X is CH₃? , ClCH₂? , Cl₃CCH₂? , and Cl₂C? CH? ) was found to follow the order: CH₃? > ClCH₂? > Cl₃C? CH₂? > Cl₂C?CH. The polymers of 4,4,4-trichlorobutylene-1,2-epoxide and its dehydrochlorination products were not vulcanizable through the chlorine functionality or the olefinic unsaturation of the type Cl₂C?CH? . The presence of an active third monomer such as allyl glycidyl ether was necessary to facilitate vulcanization. Properties of such vulcanizates are reported.     

Ethyltetramethylcyclopentadienyl complexes of cobalt,rhodium, iridium and ruthenium

Summary The syntheses of the ethyltetramethylcyclopentadienyl complexes Ru(⁵-C₅Me₄Et)(CO)₂Cl, CO( ⁵-C₅Me₄Et)(CO)₂, and [M( ⁵-C₅Me₄Et)Cl₂]₂ (M = Rh or Ir) are described; the ruthenium complex reacts with triphenylarsine to give Ru( ⁵-C₅Me₄Et)(AsPh₃)(CO)Cl.¹H and¹³C n.m.r. spectra, i.r. spectra and the physical properties of the compounds are discussed and contrasted with the known C₅H₅ and C₅Me₅ analogues.     

Mono- and dinuclear palladium(II) compounds containing nitrogen ligands. Crystal and molecular structure of [Pd(N,C-dmba)(NCO)(2,3-lut)] and [Pd(H2CCOMe)Cl(2,2′-bipy)]

The cyanate-bridged cyclopalladated compound [Pd(N,C-dmba)(-NCO)]₂ (1)(dmba = PhCH₂NMe₂) reacts in CH₂Cl₂ with 2,3-lutidine (2,3-lut), 3,4-lutidine (3,4-lut), 2,2-bipyridine (2,2-bipy) and 4,4-bipyridine (4,4-bipy), to give [Pd(N,C-dmba)(NCO)(2,3-lut)](2), [Pd(N,C-dmba)(NCO)(3,4-lut)](3), [{Pd(N,C-dmba)(NCO)}₂(-2,2-bipy)]· CH₂Cl₂ (4) and [{Pd(N,C-dmba)(NCO)}₂(-4,4-bipy)]· CH₂Cl₂ (5), respectively. The compounds were characterized by elemental analysis, i.r. and n.m.r. spectroscopy and also by t.g.a. The i.r. spectra of (2–5) display typical bands of monodentate N-bonded cyanate groups, whereas the n.m.r. data of (4) are consistent with the presence of a bridging 2,2-bipyridine ligand. Complex (4) decomposes slowly in acetone. One of the products formed, [Pd(H₂CCOMe)Cl(2,2-bipy)](6), was characterized by X-ray diffraction. As inferred from the t.g.a., the thermal stability decreases in the order:[{Pd(N,C-dmba)(NCO)}₂(-4,4-bipy)].CH₂Cl₂ (5) > [Pd(N,C-dmba)(2,3-lut)(NCO)](2)=[Pd(N,C-dmba)(3,4-lut)(NCO)](3) > [{Pd(N,C-dmba)(NCO)}₂(-2,2-bipy)]· CH₂Cl₂ (4). According to thermal analysis and X-ray diffraction patterns compounds (2–3) decompose into metallic palladium Pd(0), whereas (4–5) decompose with the formation of PdO. The X-ray crystal and molecular structure of [Pd(N,C-dmba)(NCO)(2,3-lut)](2) was determined. The lutidine unit is perpendicular to the coordination plane.     

The vibrational spectra of linear and branched perchlorosilanes Si n Cl2n+2 and their simulation using a local symmetry force field

Infrared andRaman vibrational spectra ofn-Si₄Cl₁₀,n-Si₅Cl₁₂,neo-Si₅Cl₁₂ and [(SiCl₃)₃Si]₂ have been measured and assigned. A local symmetry force field has been developed to simulate vibrational spectra of all (noncyclic) perchlorosilanes Si _n Cl_2n+2 known today (n=2, 3, 4, 5, 8). The observed spectra are reproduced satisfactorily

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Die Vibrationsspektren linearer und verzweigter PerchlorsilaneSi _n Cl _2n+2 und deren Simulierung mittels eines lokalen Symmetrie-Kraftfeldes

Zusammenfassung Infrarot- undRaman-Spektren vonn-Si₄Cl₁₀,n-Si₅Cl₁₂,neo-Si₅Cl₁₂ und [(SiCl₃)₃Si]₂ wurden aufgenommen und zugeordnet. Ein lokales Symmetrie-Kraftfeld zur Simulation der Spektren aller bisher bekannten (nicht cyclischen) Perchlorsilane Si _n Cl_2n+2 (n=2, 3, 4, 5, 8) wird angegeben. Die beobachteten Spektren werden zufriedenstellend reproduziert

     

Complexes of nickel(II) and palladium(II) with thiobenzamide

Summary The electronic and vibrational spectra of Ni^II and Pd^II complexes with thiobenzamide, L, are discussed. L acts as a sulphur donor ligand. The Pd^II compounds and (NiL₄)(ClO₄)₂ are square planar. PdL₂Cl₂ has acis-structure, while PdL₂X₂ (X=Br or I) istrans; NiL₄Cl₂ istrans-octahedral. The i.r. bands due to(M.S) and(MX) have been assigned. The influence of the anions on the properties of the complexes, both in solution and in the solid state, is discussed.     

Preparation and structure of cobalt(II), nickel(II), copper(II) and zinc(II) complexes with 3-amino-5-(α/β)pyridyl-1, 2, 4-triazoles

Summary Complexes of bidentate 3-amino-5-()-pyridyl-1,2,4-triazole (L¹) and 3-amino-5-()-pyridyl-1, 2, 4-triazole (L²) of composition [ML¹Cl₂·H₂O], [ML²Cl₂·H₂O], [ML ₃ ^2/1 Cl₂] and [ML ₃ ^2/2 Cl₂] [M=Co^II, Ni^II, Cu^II, M=Zn^II] have been prepared and characterized by elemental analyses, i.r., u.v./visible, e.s.r. spectra, magnetic moments and molar conductances.     

Symmetric binuclear complexes with an ‘end-off’ compartmental Schiff base ligand

Four binuclear transition metal(II) complexes: [Co₂L(-Cl)Cl₂] · 2H₂O, [Ni₂L(-Cl)Cl₂(H₂O)₂] · 2H₂O, [Cu₂L(-Cl)Cl₂] · 2H₂O and [Zn₂L(-Cl)Cl₂] · 2H₂O, where LH is the binucleating ligand 2,6-diformyl-4-methylphenol bis(2-hydrazino benzothiazole), were prepared. Based on the i.r. spectra, elemental analysis, conductivity measurements and thermal analysis, we propose that these complexes contain an endogenous phenoxide bridge and an exogenous chloride bridge. Magnetic and spectral data supports the existence of a weak antiferromagnetic interaction between the metal ions, and octahedral for Ni^II and a square pyramidal environment for remaining complexes. The compounds show significant growth inhibitory activity against the fungi, Aspergillus niger and Candida albicans, as compared to antibacterial activity against Bacillus cirroflagellosus and Pseudomonas auregenosa.     

Studies on platinum(II) and palladium(II) complexes of some N,N′-disubstituted thiourea derivatives

Summary A series of new Pt^II and Pd^II complexes of N,N-disubstituted thiourea derivatives of general formulae [MLCl₂]₂, [ML₂Cl₂] and [ML₄]Cl₂ have been prepared and characterised by physicochemical and spectroscopic methods. The reaction of these ligands with [M(DMSO)₂Cl₂], M = Pt, cis- or Pd, trans-, in CHCl₃ and EtOH at ambient temperature or under reflux, is described.     

Octahedral ruthenium(II) alkenyl complexes containing {\text{N}}{\text{S}} coordinated heterocyclic ligands

Summary Hexacoordinated ruthenium(II) alkenyl complexes of the type Ru(CO)(CR=CHPh)( )(PPh₃)₂ have been prepared from coordinately unsaturated -vinyl complexes [Ru(CO)Cl(CR=CHPh)(PPh₃)₂] (R = H or Ph) and the sodio-derivative of the containing heterocyclic ligands [ = 3,4-substituted 1,2,4-triazole-5-thione and 5-alkylthio-1,3,4-thiadiazole-2-thione] in a CH₂Cl₂/MeOH mixture at ambient temperature. The complexes were characterized by their elemental analysis, i.r., ¹H and ³¹P n.m.r. spectra. An octahedral structure with transphosphorus ligands has been assigned on the basis of the spectral data.     

Coordination compounds of palladium(II) and platinum(II) with benzotriazoles

Summary The nitrogen-donor ligands 1-methylbenzotriazole (1Mebta), 5-methylbenzotriazole (5MebtaH), 5-chlorobenzotriazole (5ClbtaH) and 5-nitrobenzotriazole (5NO₂btaH) react with palladium(II) and platinum(II) to give cis-[PdL₂Cl₂], cis-[PtL₂Cl₂] (L = 1Mebta, 5MebtaH, 5ClbtaH or 5NO₂btaH), [Pt(5ClbtaH)₄]Cl₂, [Pd-(5MebtaH)Cl₂]₂, [Pd(5ClbtaH)Cl₂]₂ and [Pd(5NO₂btaH)-Cl₂]₂. The complexes were characterized by physicochemical and spectroscopic methods. The benzotriazoles act as monodentate ligands binding through N(3). Monomeric square planar structures are assigned for the 12 complexes and [Pt(5ClbtaH)₄]Cl₂ in the solid state. Centrosymmetric, chloro-bridged, dinuclear square planar structures of C_2h symmetry are proposed for the 11 palladium(II) compounds.     

Mitteilung der Abteilung für Anorganische Chemie der IUPAC

Metal Complexes with Anionic Ligands of Elements of the Main Group IV. IV. Homogenous and Heterogenous Transition Metal Complexes of the Dichlorobromo-, Dibromochloro-, and Tribromostannide Ligands Monosubstituted complexes of the type [M(CO)₅SnBr_3?nCl_n]^? are formed if the hexacarbonyls of chromium, molybdenum, and tungsten are reacted with halogenostannide ions SnBr_3?nCl (n = 0, 1, 2). The reactions of dibenzene chromium and this stannide ions yield homogenous hexakis(trihalogenostannide)chromate(0) complexes [Cr(SnBr_3?nCl_n)₆]^6? (n = 1, 2). Both types of chromate(0) ions are isolated as salts with the cation [N(C₂H₅)₄]⁺. The behaviour of SnBr_3?nCl (n = 0–3) as ligands is discussed, the i. r. spectra of their metalcarbonyl derivatives are reported.     

Cobalt(II), nickel(II) and copper(II) complexes withN-cyano-N′-methyl-N″(2-[(5-methyl-1H-imidazol-4-yl)methylthio]ethyl)guanidine

Summary N-Cyano-N-methyl-N(2-[(5-methyl-1H-imidazol-4-yl)-methylthio] ethyl) guanidine cimetidine (CM), complexes with Co^II, Ni^II and Cu^II are described. The compounds are of stoichiometry [M(CM)₂]SO₄ · nH₂O [M = Co^II, Ni^II or Cu^II; n = 3,3 or 4, respectively], [M(CM)₂](ClO₄)₂ [M = Co^II or Ni^II], [M(CM)₂]Cl₂ · nH₂O [M=Co^II, Ni^II or Cu^II; n = 1, 2, or 2, respectively] and [Cu(CM)SO₄] · 2H₂O. The electronic spectra of the compounds in solid state, magnetic susceptibilities and i.r. and e.p.r. spectra were studied. Octahedral environments are proposed for the complexes: [M(CM)₂]SO₄·nH₂O, [M(CM)₂](ClO₄)₂, [Ni(CM)₂]Cl₂ · 2H₂O, [Cu(CM)₂]Cl₂ · 2H₂O and [Cu(CM)SO₄] · 2H₂O and a tetrahedral structure for [Co(CM)₂]Cl₂ · H₂O.     

Studies on mixed ligand complexes,part 5. Heterochelate complexes of cobalt(III) derived from the quadridentate NNNN donor ligand triethylenetetramine and bidentate OO,ON and NN donor ligands

Summary A series of new cobalt(III) complexes of general formula [Co(AA)(trien)]X_n (where AA = tropolone, acetoacetanilide, ethylacetoacetate, biguanide, 2-guanidinobenzimidazole, propylenediamine, picolylamine, 2,2-dipyridyl, 3-aminopyridine, picolinic acid and quinaldinic acid, trien = triethylenetetramine, X=Cl^–, Br^–, I^– and n=2–3) have been synthesized and characterized by elemental analysis, electronic and i.r. spectra, equivalent weight, conductance and magnetic measurements. The electronic spectra of the complexes exhibit one or two ligand field bands atca. 20000 and 29000 cm^–1 due to the¹ A _1g ¹ T _1g and¹ A _1g ¹ T _2g transitions respectively. Conductance measurements indicate the triunivalent nature of [Co(tropolone)(trien)]I₃, [Co(picolylamine)(trien)]I₃, [Co(3-aminopyridine)(trien)]I₃, [Co(2,2-dipyridyl)(trien)]Cl₃, [Co(biguanide)(trien)]I₃, [Co(propylenediamine)(trien)]I₃ and biunivalent nature of [Co(picolinate)(trien)]Cl₂, [Co(quinaldinate)(trien)]Cl₂, [Co(acetoacetanilido)(trien)]Cl₂, and [Co(ethylacetoacetato)(trien)]I₂. Equivalent weight determination by the ion-exchange resin (H⁺ form) method gives the values of molecular weights which are consistent with the theory. The complexes are diamagnetic.     

M3S2Cl5 (M = Nd,Dy): Zwei Formen von Sulfidchloriden des Neodyms und Dysprosiums mit Doppelketten 1∞{[S2M3]5+} kantenverknüpfter [SM4]‐Tetraeder

M₃S₂Cl₅ (M = Nd, Dy): Two Types of Neodymium and Dysprosium Sulfide Chlorides with Double Chains ¹_∞{[S₂M₃]⁵⁺} of Edge‐Sharing [SM₄] Tetrahedra Nd₃S₂Cl₅ (monoclinic, P2₁/c; a = 2176.9(2), b = 654.62(6), c = 703.91(7) pm, β = 97.879(8)°; Z = 4) and Dy₃S₂Cl₅ (orthorhombic, Pnma; a = 682.34(7), b = 2153.2(2), c = 638.21(6) pm; Z = 4) are formed by reacting neodymium or dysprosium metal with sulfur and the respective trichloride (MCl₃) in suitable molar ratios (M : S : MCl₃ = 4 : 6 : 5) within ten days in evacuated silica tubes at 850 °C. The crystal structure of Dy₃S₂Cl₅ (P 2₁/n 2₁/m 2₁/a) can be transferred to that of Nd₃S₂Cl₅ (P 1 1 2₁/a ≡ P 1 2₁/c 1) through a lattice‐equivalent transition of the index 2 (t2) by the loss of two screw axes, one diagonal glide plane, and one simple mirror plane. The moisture sensitive, transparent, pale violet (Nd₃S₂Cl₅) or faint yellow (Dy₃S₂Cl₅) sulfide chlorides both exhibit infinite double strands {[S₂M₃]⁵⁺} (M = Nd, Dy) as main structural feature, which can be built of two condensed anti‐SiS₂‐analogous chains of trans‐edge sharing [SM₄] tetrahedra. These are running parallel [001] in Nd₃S₂Cl₅ or [100] in Dy₃S₂Cl₅ and arrange as a hexagonal closest packing of rods. The coordination polyhedra about the M³⁺ cations can be described as bicapped trigonal prisms (CN = 8) in both crystal structures, where by the collapse of two symmetrically equivalent particles the total number of three in the case of Nd₃S₂Cl₅ is reduced to two crystallographically different ones in Dy₃S₂Cl₅. Correspondingly, only three independent Cl^– anions are present in the crystal structure of Dy₃S₂Cl₅ for charge compensation and three‐dimensional cross‐linkage of the {[S₂M₃]⁵⁺} strands as compared to five in Nd₃S₂Cl₅. The analogue holds for the S^2–anions: The two distinct ones in the monoclinic Nd₃S₂Cl₅ structure unite to a single one in orthorhombic Dy₃S₂Cl₅.     

Verdampfung von Kupfer(II)chlorid und Struktur des Dampfes untersucht mit UV./VIS.- und Raman-Spektroskopie

The vapour pressure of CuCl₂ and the dimerization of CuCl₂(g) have been investigated by optical spectroscopy in the range 420–650°C, p = 0.5-5 atm. The enthalpy of dimerization of CuCl₂(g) was determined by visible and by Raman spectroscopy and good agreement was found (?154 kJmol^?1 and ?143 kJmol^?1). CuCl₂(g) shows two totally symmetric Raman modes (373 and 127 cm^?1) indicating that, at least at elevated temperatures, CuCl₂(g) is not a linear molecule. The optical spectra of Cu₂Cl₄(g) and CuLCl₅(g) (L ? Ga, In) are very similar supporting a CuCl₃-chromophor in both cases. The formerly proposed structure of CuL₂Cl₈(g) (L ? Al, Ga) contains bridging and terminal chlorides, structural elements also present in Cu₂Cl₄(g). In agreement with the proposed structure v is identical in Cu₂Cl₄(g) and CuL₂Cl₈(g), while V is at lower energies (20–30 cm^?1) in CuL₂Cl₈(g) than in Cu₂Cl₄(g).     

Mixed ligand complexes of palladium(II) and platinum(II) with methionine and 2,4-disubstituted pyrimidines

Summary Mixed ligand complexes ofcis-[M(MetH)Cl₂] (M=Pd²⁺ and Pt²⁺; MetH=methionine) with 2,4-disubstituted pyrimidines were prepared and characterised. Thecis-[Pd(MetH)Cl₂] complex reacted with cytosine (2-hydroxy-4-aminopyrimidine), isocytosine (2-amino-4-hydroxypyrimidine) and thiocytosine (2-thio-4-amino-pyrimidine) to form ternary complexes.cis-[Pt(MetH)Cl₂] however reacted with cytosine, uracil (2,4-pyrimidine dione or 2,4-dihydroxypyrimidine) to yield the corresponding mixed ligand complexes. The primary ligand, methionine, binds to the metal ion through sulphur and amino nitrogenvia a six membered chelate ring. The secondary ligands (substituted pyrimidines) bind to the Pd²⁺ or Pt²⁺ metal ion through the ring nitrogen (N₃), as monodentate ligand. Thiocytosine however acts as a bidentate ligand, coordinating to the metal ion through-SH and ring nitrogen (N₃). All complexes are 11 electrolytes, except the thiocytosine complex, which is a 12 electrolyte.