A new approach to the synthesis of oligomers. Application to the synthesis of p-phenylene thioether wires

Oligothioethers 4-RC₆H₄(SC₆H₄-4)_nX (n = 1-3; X = Br, I; R = NO₂; X = Br; R = MeO. n = 1 and 2; X = I; R = MeO. n = 4; X = Br; R = NO₂) have been prepared through a process involving (i) palladium-catalyzed C-S coupling between 4-RC₆H₄(SC₆H₄-4)_n−1I and 4-BrC₆H₄SH to give 4-RC₆H₄(SC₆H₄-4)_nBr and (ii) copper-catalyzed replacement of Br by I.     

Über diphenyl- und bis(3-nitrophenyl)bleidihalogenide und über bis(3-nitrophenyl)bleihalogenokomplexe

Diaryllead dihalides R₂PbX₂ may be prepared easily by treatment of R₂Pb(OAc)₂ (OAcCH₃COO) with HX in acetic acid (R = C₆H₅; X = F, Cl, Br, I. R = 3-NO₂C₆H₄; X = Br, I). (3-NO₂C₆H₄)₂Pb(OAc)₂ forms soluble complexes when dissolved in acetic acid containing an excess of HX; (3-NO₂C₆H₄)₂PbCl₂ may be isolated from those solutions. Treatment of these solutions with CsOAc and [(C₆H₅)₄P]X, respectively, yield the complex salts M_n[(3-NO₂C₅H₄)₂PbX_2+n] (X = Cl; M = Cs, (C₆H₅)₄P; n = 0.5. X = Br; M = Cs; n = 0.5. M = (C₆H₅)₄P; n = 2, as acetic acid solvate).In addition the preparations of [(C₆H₅)₄P]_n[(3-NO₂C₆H₄)₂PbX_2+n] (X = Cl; n = 1. X = Br; n = 1, 2, as acetone solvate) and of (3-NO₂C₆H₄)₂PbF₂ (as hydrate) are described.     

Darstellung und schwingungsspektroskopische Untersuchungen von Alkyl- und Arylborhalogeniden

Preparation and Vibrational Spectra of Alkyl- and Arylboronhalides Organohaloboranes R_mBX_3?m (R = CH₃, C₂H₅; X = Cl, Br; m = 1–3) can be prepared from BX₃ and tetraalkyllead as alkylating agent Data of the vibrational spectra (i.r. and Raman) of R_nBY_3?n (Y = F, Cl and Br; n = 1–3) and C₆H₅BY₂ are tabulated and assigned. Mixed halides i. e. RBXY compounds are spectroscopically characterized.     

Alkoxy,amido and thiolato complexes of tris (3, 5-dimethylpyrazolyl)borato(nitrosyl) molybdenum fluoride,chloride and bromide

The complexes Mo{HB(Me₂pyz)₃}(NO)XY {HB(Me₂pyz)₃  HB(3, 5-Me₂C₃HN₂)₃; X=Y=F, Cl or Br; X=F, Y=OEt, NHMe or SBuⁿ; X=Cl, Y=NHR (R=Me Et, Buⁿ, Ph, p-MeC₆H₄), NMe₂ and SR (R=Buⁿ, C₆H₁₁, CH₂Ph, Ph); X=Br, Y=NHMe, NMe₂ and SBuⁿ} have been prepared and characterised spectroscopically. Their properties are generally similar to those of their iodo-analogues.     

Schiff base of 0-methylthioaniline and salicylaldehyde and its metal chelates

The Schiff base salicylideneamino-o-methylthiobenzene (I), CH₃S?C₆H₄?N=CH?C₆H₄?OH (SMeNOH), has been synthesized and its complexes of the type CuX(SMeNO) whereX=Cl, Br, NO₃, CNS, and ClO₄, CuX′(SMeNOH) whereX′=SO₄ and (BF₄)₂, NiX″ ₂(SMeNOH) whereX″=Cl and Br, NiNO₃(SMeNO) andM(SMeNO) ₂ whereM=Cu, Ni and Co, have been prepared and characterised through infrared, magnetic moment and conductance measurements.     

Intermolecular dehydration of alcohols by the action of copper compounds activated with carbon tetrabromide. Synthesis of ethers

Copper compounds of the general formula CuX _n (X = Cl, Br, I, acac, OAc, C₇H₄O₃, C₇H₅O₂; n = 1, 2) activated by carbon tetrabromide catalyzed intermolecular dehydration of primary and secondary alcohols with formation of the corresponding ethers.     

Polarographie de quelques halogénures organostanniques dans le diméthylformamide

The polarographic behavior of compounds R_nSnX_4?n with R=CH₃, C₂H₅, C₆H₅; X=Cl,Br and n=0–3, on a dropping Hg electrode, in dimethylformamide, has been examined and for all cases, reduction pathways have been proposed; the most important features being: the disappearance of the second one-electron step for chlorotrimethyl(ethyl)tin, the observation of two one-electron steps for R₂SnBr₂ dibromides, the easy complexation of R₂SnCl₂ and RSnCl₃ compounds by chloride ions, and the discrete steps involving 2 and 1 electrons for tribromo(ethyl)tin.     

Substitutions of organopalladium(II) species with benzimidazole derivatives

The [Pd(cod)(cotl)]ClO₄ complex (cod = cycloocta-1,5-diene; cotl = cyclooctenyl, C₁₈H₁₃ ^–) undergoes substitutions with new Schiff base ligands containing benzimidazole L [L = 2-(2-N-n-propylidenephenyl)benzimidazole (L¹); 2-(2-N-i-propylidenephenyl)benzimidazole (L²); 2-(2-N-n-butylidenephenyl)benzimidazole (L³); 2-(2-N-i-butylidenephenyl)benzimidazole (L⁴)]. Facile displacement of cod by L occurs to produce complexes of the type [Pd(cotl)L]ClO₄· nMe₂CO (n= 0; L = L¹, L² or L³; n= 2, L = L⁴). Dihalobridge complexes of the type [Pd(cotl)X]₂(X = Cl or Br) undergo halogen-bridge cleavage with L¹–L⁴ to give mononuclear complexes of the type Pd(cotl)LX · nH₂O (n= 2, X = Cl, L = L¹; n= 0, X = Br, L = L¹; n= 0, X = Cl, L = L²; n= 0, X = Cl or Br, L = L³; n= 0, X = Cl, L = L⁴; n= 2, X = Br, L = L⁴) and a binuclear complex [Pd(cotl)Br]₂L². The complexes were characterised by physical properties, i.r., ¹H- and ¹³C-n.m.r. spectral techniques and by mass spectra. Probable structures have been proposed.     

Organotin compounds bearing mesogenic sidechains: synthesis, X-ray structures and polymerisation chemistry

Organotin compounds R₃Sn(CH₂)_n+2OC₆H₄C₆H₄Y (R₃=Ph₃, Ph₂Bu; Y=H, CN; n=1-3) and RX₂Sn(CH₂)_n+2OC₆H₄C₆H₄Y (R=Ph, Bu; Y=H, CN; X=Br, I; n=1-3) have been synthesised and characterised by ¹H-, ¹³C-, ¹¹⁹Sn-NMR and Mössbauer spectroscopies. X-ray crystallography reveals tetrahedral geometries for Ph₃Sn(CH₂)₄OC₆H₄C₆H₅ and Ph₃Sn(CH₂)₃OC₆H₄C₆H₄CN, a six-coordinated, bromine-bridged dimeric structure for PhBr₂Sn(CH₂)₃OC₆H₄C₆H₅ containing a mer-Br₃C₂OSn coordination sphere about tin and a five-coordinated monomeric structure for PhBr₂Sn(CH₂)₃OC₆H₄C₆H₄CN. In all cases there is strong alignment of mesogenic groups in the solid-state but only PhBr₂Sn(CH₂)₃OC₆H₄C₆H₄CN shows any indication of liquid-crystal behaviour. Wurtz polymerisation of RBr₂Sn(CH₂)₅OC₆H₄C₆H₅ (R=Ph, Bu), both of which contain non-chelating ether functions, generated polystannanes (RR′Sn)_n with M_n 2.3×10⁵; M_w 3.0×10⁵; M_w/M_n 1.30 and M_n 1.3×10⁵; M_w 2.5×10⁵; M_w/M_n 1.96, respectively, while no polymer was obtained from chelated PhBr₂Sn(CH₂)₃OC₆H₄C₆H₅     

Cleavage of the sulfur-sulfur bond in 2,4-dinitrophenyl 4-substituted phenyl disulfides by trans-[IrX(CO)(PPh3)2]

A series of 2,4-dinitrophenyl 4-Y-phenyl disulfides (Y=NO₂, Br, F, H, CH₃, or CH₃O) have been shown to react with trans-IrX(CO)(PPh₃)₂ (X=Cl, Br, or I) in refluxing benzene to form “oxidative-elimination” products of the type, [IrX(SC₆h₄Y)(SC₆H₃(NO₂)₂)(CO)(PPh₃)]₂. The physical properties of these complexes are discussed in relation to their structure in the solid state and in solution. In particular, available infrared spectral data indicate that these complexes contain 2,4-dinitrobenzenethiolato bridging groups and that the substituted arenethiolato ligand is trans to carbon monoxide.     

Dithiocarbamate Complexes of Nickel(II) with 1,1′-Bis(Diphenylphosphino) Ferrocene

Ni(II) complexes of composition [Ni(bzⁱprdtc)(dppf)]X, [Ni(but₂dtc)(dppf)]X and [Ni(Rdtc)(dppf)]X [bz = C₇H₇; ⁱpr = C₃H₇; but = C₄H₉; R = pld = C₄H₈; tz = C₃H₆S; hmi = C₆H₁₂; dtc = S₂CN; dppf = 1,1'-bis(diphenylphosphino)ferrocene C₃₄H₂₈P₂Fe; X = ClO₄, I, Br, NCS] were synthesized and characterized X-ray structural analysis of [Ni(hmidtc)(dppf)]ClO₄ confirmed coordination number four for nickel in a distorted, square-planar, NiS₂P₂ arrangement     

Electronic effects in octahedral π-allyliron complexes: 13C NMR spectra

¹³C NMR spectra have been studied for the three series of allyliron derivatives: (i) C₃HP₅Fe(CO)₃X (X = I, Br, Cl, ONO₂, OCOCH₃, OCOCF₃); (ii) 2-RC₃H₄Fe(CO)₃X (R = CH₃, Br; X = I, Br, Cl, ONO₂, OCOCF₃), and (iii) 1-RC₃H₄Fe(CO)₃X (R = CH₃, C₆H₅; X = Br, Cl, OCOCF₃). The spectra reveal the effect of the nature of the ligand X and substituent R on the chemical shifts of the allyl and carbonyl carbon atoms.     

Reactions of metal carbonyl derivatives : XI. Tertiary phosphine,phosphite and stibine and ditertiaryphosphine and arsine derivatives of bis(μ-phenyl- sulphidotricarbonyliron)

The ditertiary phosphines (C₆H₅)₂P(CH₂)_nP(C₆H₅)₂ (n = 1 and 2), cis(C₆H₅)₂PC₂H₂P(C₆H₅)₂ and (C₆H₅)₂PN(C₂H₅)P(C₆H₅₂ and the ditertiary arsines (C₆H₅)₂As(CH₂)_nAs(C₆H₅)2 (_n = 1 and 2) react with [Fe(CO)₃SC₆H₅]₂ to give a wide range of products, the nature of which depends on the reaction conditions and the ligand involved. Examples of the different types of comp isolated include, (i) Fe₂(CO)₅[(C₆H₅)₂PCH₂P(C₆H₅)₂](SC₆H₅)₂, in which the ligand acts as a monodentate, (ii) {[Fe(CO)₂SC₆H₅]₂[(C₆H₅)₂PC₂H₄P(C₆H₅)₂]}₂, in which two [Fe(CO)₂SC₆H₅]₂ moieties are bridged by two diphosphine ligands, (iii) [Fe(CO)₂SC₆H₅]₂[(C₆H₅)₂PN(C₂H₅)P(C₆H₅)₂], in which the ligand bridges the two iron atoms, and (iv) Fe(CO)₃(SC₆H₅)₂Fe(CO)[(C₆H₅)₂PC₂H₂P(C₆H₅)₂], which contains the ligand chelated to a single iron atom. The tertiary phosphines PR₃ (R=C₂H₅ and C₆H₅), phosphites P(OR′)₃(R′ = CH₃, C₂H₅, i-C₃H₇ and C₆H₅) and the stibine Sb(C₆H₅)₃ bring about mono-, bis- or tris-substitution in [Fe(CO)₃SC₆H₅]₂ depending on the reaction conditions and the ligand involved. Whereas in solution [Fe(CO)₂L(SC₆H₅)]₂ [L = PR₃ (R = C₂H₅ and C₆H₅), P(OC₆H₅)₃ and Sb(C₆H₅)₃] exist as a single isomer, [Fe(CO)₂L′(SC₆H₅)]₂ [L′=P(OR′)₃ (R'=CH₃, C₂H₅ and i-C₃H₇)] occur as a mixture of isomers.     

ortho-, meta- and para-nitrophenylgold(I) complexes

Treatment of [BzPh₃P][AuCl₂] with [Hg(x-C₆H₄NO₂)₂] (x = o, m, or p) gives anionic gold(I) complexes of the type [BzPh₃P][Au(R)Cl](R = o-, m- or p-C₆H₄NO₂, Bz = C₆H₅CH₂). The chloro ligand in [Au(o-C₆H₄NO₂)Cl]^? can be replaced by bromo or iodo ligands by use of NaBr or NaI. The anions [Au(R)Cl]^? react with neutral monodentate ligands, L, to give neutral mononuclear complexes [Au(R)L] (R = o-C₆H₄NO₂, L = PPh₃, AsPh₃; R = m-C₆H₄NO₂, L = PPh₃) and with 1,2-bis(diphenylphosphino)ethane (dpe) to give [Au₂(R)₂(dpe)] (R = o-C₆H₄NO₂). The corresponding [Au(p-C₆H₄NO₂)Cl]^? reacts with PPh₃ or AsPh₃ to give mixtures containing [AuClL]. The anionic ortho-nitrophenylgold(I) complex is much more stable than its meta- or para-nitrophenyl isomers. These are thought to be the first reports of nitrophenylgold(I) complexes.     

Novel heterocyclic selenazadiphospholaminediselenides, zwitterionic carbamidoyl(phenyl)-phosphinodiselenoic acids and selenoureas derived from cyanamides

2,4-Bis(phenyl)-1,3-diselenadiphosphetane-2,4-diselenide (Woollins’ reagent, WR) reacts with cyanamides (1a-h) in refluxing toluene to afford a series of novel selenazadiphospholaminediselenides (RR′NCN(PhP(Se)SeP(Se)Ph, R=C₆H₅(CH₂)_1-3, 4-n-C₁₀H₂₁C₆H₄ and 4-BrC₆H₄CH₂; R′=H, CH₃, C₂H₅ and C(O)OC₂H₅2a-g). Post-treatment of the reaction mixture with water led to the formation of carbamidoyl(phenyl)phosphinodiselenoic acids (RR′NC(NH₂)P(SeH)₂Ph, R=C₆H₅(CH₂)_2-3, 4-n-C₁₀H₂₁C₆H₄ and 4-BrC₆H₄CH₂; R′=H and CH₃, 3b, 3c, 3e and 3f) and selenoureas (RR′NC(Se)NH₂, R=C₆H₅(CH)_1-2; R′=CH₃ and OC(O)C₂H₅, 4f and 4h) in moderate to excellent yields. All new compounds are characterised spectroscopically and five X-ray crystal structures are reported.     

Coordination compounds of cobalt, nickel, copper and zinc with thiosemicarbazone and 3-phenylpropenal semicarbazone

Hydrates of 3-phenylpropenal thiosemicarbazone (HL·H₂O) and semicarbazone (HL′·H₂O) react in methanol with cobalt, nickel, copper, and zinc chlorides, nitrates, and acetates to form coordination compounds MX₂·2HL·nSolv [M = Co, Ni, Cu, Zn; X = Cl, NO₃; HL = C₆H₅CH=CH-CH=N-NHC(O)NH₂; n = 0–3; Solv = H₂O, CH₃OH], CuX₂·HL·nH₂O [M = Ni, Cu; n = 0, 1], ML₂·nH₂O and ML′·nH₂O [M = Co, Ni, Zn; HL′ = C₆H₅CH=CH-CH=N-NHC(O)NH₂; n = 0–3]. In the presence of amines (A = C₅H₅N, 2-CH₃C₅H₄N, 3-CH₃C₅H₄N, and 4-CH₃C₅H₄N) these reactions yield the complexes Cu(A)LCl·CH₃OH and M(A)LX·nH₂O [M = Cu, Ni; X = Cl, NO₃; n = 0–2]. The copper complexes with the amine ligands are of polynuclear structure, and other complexes are monomeric. Carbazones (HL and HL′) are included in the complexes as bidentate N,S-and N,O-ligands. The thermolysis of the complexes involves the stages of removing solvent crystallization molecules (70–90°C), deaquation (150–170°C), and full thermal decomposition (500–580°C).     

PMR of complexes of organohalostannanes with N-vinyl-N-ethylimidazole

The chemical shifts and spin-spin coupling constants of the protons of the vinyl and ethyl groups and of the imidazole ring in the PMR spectra of complexes R_4–n·SnX_n · mB, where R=C₂H₅, C₄H₉;X=Cl, Br, I; B is N-vinylimidazole or N-ethylimidazole; and n=1 (m=1) and 2 (m=2), are compared. The electronic and geometrical structures of these complexes are discussed.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 3, pp. 391–394, March, 1973.     

Reactions of some fluoroaromatics with the ethoxide anion

The reactions of sodium ethoxide in ethanol with various fluoroaromatics, C₆F_6?nH_n, C₆F_5?nH_nNO₂, C₆F₅X (X = CF₃, C₆F₅, COCH₃, CH₂Br), C₆Cl₆ and $\text{m}$H₂C₆Cl₄ have been studied. Partial substitution of the aromatic halogen was observed. The new products have been characterized by elemental analysis, NMR (H?1 and F?19), infrared and mass spectroscopy.     

Protonation of the metal—metal bond in Fe2(μ-A)(μ-A′)(CO)4L2 complexes (A  A′ SC6H5, P(C6H5)2, P(CH3)2; A  SC6H5, A′ z.dbnd; P(C6H5)2; L z.dbnd; P(C6H5)3-n(CH3)n). : III. Experimental study of the influence of the A and A′ bridges on the basicity of the metal—metal bond

In order to check the influence of the bridges on the basicity of the metal—metal bond in Fe₂(μ-A)(μ-A′)(CO)₄L₂ complexes, the compounds with A  A′ SC₆H₅, P(C₆H₅)₂; P(CH₃)₂; A  SC₅H₅, A′ P(C₆H₅)₂ and L  P(CH₃)_3-n (C₆H₅)_n (n  0—3) have been prepared. IR and PMR spectroscopic results are interpreted in structural terms, and show that the Fe₂(SC₆H₅)(P(C₆H₅)₂.)-(CO)₄L₂ complexes are non rigid on the NMR time scale for n = 0, 1. Replacement of the first SC₆H₅ bridge by a P(C₆H₅)₂ bridge markedly increase the basicity of the metal—metal bond, but replacement of the second SC₆H₅ bridge has no significant effect.     

Metal complexes of hybrid oxygen-arsenic ligands—III : Complexes of 2-tertiary arsinobenzoic acids with zinc(II), cadmium(II) and mercury(II). Discovery of a novel chelating system

This paper describes the preparation of the halogeno complexes, HgX₂(o-R₂AsC₆H₄CO₂H) (X = Cl, Br, I, and R = Et; X = Br, I, and R-C₆H₁₁) and the carboxylate complexes, M(o-R₂-AsC₆H₄CO₂)₂nL(M = Cd, R = Et, C₆H₁₁ and n = O; M = Zn; R = Et; nL = H₂O; M = Zn, R = C₆H₁₁, nL = 3H₂O; M = Hg, R = p-tolyl, nL = 2H₂O; M = Hg, R = Me, Ph; C₆H₁₁ and nL = EtOH). The structures already reported for the halogeno complexes with R = Ph, Me, p-tolyl and X = Cl, Br, I, have been revised on the basis of detailed scrutiny of the IR spectral data and all these complexes have been divided into four structural types out of which three retain the acid dimer unit of the free ligand. In the carboxylate complexes the lowering of ν_s, CO₂ band and the marginal change in the ν_as CO₂ band with respect to those of the corresponding ligand sodium salts have been attributed to the existence of a novel resonating chelating system with the possibility of having a ring current.