Spezielle Organoschwefel- und -selenverbindungen einiger Übergangsmetalle

Aluminum phenylselenolate and 1-naphthylselenolat react with TiCl₄, ZrCl₄, NbCl₅, TaCl₅, WCl₆ and CrCl₃ · 3THF giving compounds of types M(SeR)₄ (M = Ti, Zr, W; R = C₆H₅, C₁₀H₇) and M(SeR)₃ (M = Nb, Ta, Cr; R = C₆H₅, C₁₀H₇). By reaction of nickel(II), cobalt(II) and cobalt(III) acetylacetonates with thiophenol, selenophenol and 1-selenonaphthol polymeric compounds of composition Ni(XR)₂, Co(XR)_n (X = S, Se; R = C₆H₅, C₁₀H₇; n = 2 or 3) and Co(SC₆H₅)₂ · C₆H₅SH are obtained. [(n-C₄H₉)₃P]₂NiCl₂ and selenophenol in the presence of triethylamine give the monomeric compound [(n-C₄H₉)₃P]₂Ni(SeC₆H₅)₂.     

Direktsynthese von orthometallierten Ketonen des Typs RCO (o-C6H4)Mn(CO)4−nLn (R = Alkyl- und Arylrest,n = 0, 1, 2, L = Ligand)

Direct Synthesis of Orthometallated Ketones of the Type RCO(o-C₆H₄)Mn(CO)_4?nL_n (R = Alkyl and Aryl Groups, n = 0, 1, 2, L = Ligand) The starting materials of the type RMn(CO)_5?nL_n und (C₆H₅)₂ Hg react to the products of the type RCO(o-C₆H₄)Mn(CO)_4?nL_n[n = 0, R = Ch₃, C₂H₅, C₃H₇, C₆H₅,CH₂; R = C₆H₅, n = 1, L = E(C₆H₅)₃, E = P, As, Sb; R = C₆H₅, n = 2, L = P(OR′)₃, R′ = C₆H₅, CH₃, C₂H₅, C₃H₇]. Steps of their complex reaction pathway are proposed. These orthometallated substances have been characterized by means of ¹H-n.m.r., i.r. and u.v. spectroscopic measurements. The determination of the molecular structure of the two compounds RCO(o-C₆H₄)Mn(CO)₃L [R = C₂H₅, L = CO; R = C₆H₅, L = As(C₆H₅)₃] show that both contain a planar heterocyclic five-membered ring of the type .     

Carbamoyl and alkoxycarbonyl complexes of palladium(II) and platinum(II)

Carbamoyl and alkoxycarbonyl complexes of palladium(II) and platinum(II) of the type M(pnp)(CONHR)Cl (pnp = 2,6-bis(diphenylphosphinomethyl)pyridine; M Pd, R  C₆H₅, p-CH₃C₆H₄, p-CH₃OC₆H₄, C₆H₁₁, t-Bu; M  Pt, R  C₆H₅), Pd(pnp)[CON(Pr)₂]Cl (Pr = propyl), M(pnp)(COOR)Cl (M  Pd, R  C₆H₅, CH₃; M  Pt, R  CH₃), Pd(pnp)(COOCH₃)₂ result from reaction of M(pnp)Cl₂ with carbon monoxide and amines or alkoxides at room temperature and atmospheric pressure.The carbamoyl complexes react with bases to give urethane or diphenylurea depending upon the experimental conditions.     

Organo group VB chemistry: Part VI. On the electric dipole moments of some substituted tertiary phenylphosphines, -arsines, -stibines and -bismuthines

The dipole moments of the following series of tertiary substituted aryl-group VB compounds were measured: (a) (C₆H₅)₃M and (XC₆H₄)₃M with M = P, As, Sb, Bi and X = 4-F, 4-Cl, 4-CH₃, 3-F, 3-Cl; and (b) (3-XC₆H₄)_3?n PR_n with R = C₆H₅, 4-FC₆H₄ and X = F, Cl. These experimental molecular moments are discussed as a consistent set of data that allows the calculation, within the framework of the vectorial additive method, of suitable group moments, bond moments and configurational parameters.     

KRISTALLSTRUKTUR VON BIS(DIETHYLDITHIOCARBAMATO)-PHENYLPHOSPHAN UND SYNTHESE EINIGER MONO- UND BIS(DIORGANYLDITHIOCARBAMATO)PHOSPHANE

Abstract

By reaction of organylchlorophosphanes with sodium dithiocarbamates compounds of the type RP(S₂CNR₂′)₂ with R = CH₃, C₆H₅; R' = CH₃, C₂H₅, CH(CH₃)₂, C₆H₅ and of the type (C₆H₅)₂PS₂CNR₂′ with R' = CH₃, CH(CH₃)₂ as well as compound [(C₆H₅)₂PS₂CN(CH₃)CH₂-]₂ are obtained. The crystal structure of C₆H₅P(S₂CN(C₂H₅)₂)₂ shows that the trend from bidentate to monodentate bonding of the dithiocarbamate ligands in the homologous series RE(S₂CN(C₂H₅)₂)₂; E = Bi, Sb, As, P is continued for E = P.

Durch Umsetzung der jeweiligen Chlorophosphane mit den entsprechenden Natriumdithiocarbamaten können folgende Verbindungen erhalten werden: Verbindungen des Typs RP(S₂CNR₂′)₂ mit R = CH₃, C₆H₅; R' = CH₃, C₂H₅, CH(CH₃)₂, C₆H₅; Verbindungen des Typs (C₆H₅)₂PS₂CNR₂′ mit R' = CH₃, CH(CH₃)₂ sowie [(C₆H₅)₂PS₂CN(CH₃)CH₂-]₂. Die Kristallstruktur von C₆H₅P(S₂CN(C₂H₅)₂)₂ zeigt, daß sich der Trend zu schwächer ausgeprägter zweizähniger Bindungsweise der Dithiocarbamatliganden in der homologen Reihe RE(S₂CN(C₂H₅)₂)₂; E = Bi, Sb, As, P für E = P fortsetzt.     

Über die Darstellung von Tricyanmethanidometallbromiden und Organometalltricyanmethaniden durch Reaktionen mit Bromtricyanmethan BrC(CN)3

Different reactions of BrC(CN)₃ with metal bromides (MBr₄; M = Sn, Ti, Zr), metal organyles (SnR₄, MR₂ (R = C₂H₅, C₆H₅; M = Zn, Cd), C₆H₅HgBr) and with phosphorus tribromide are reported. These reactions lead to the formation of new compounds of the types MBr₃NCC(CN)₂, R₃MNCC(CN)₂, RMNCC(CN)₂ and PBr₄NCC(CN)₂, respectively. The structures of the new compounds are discussed, using results of infrared spectroscopic measurements. Mostly the pseudohalide group C(CN)₃ is bonded to the metal via the nitrogen of a cyano group. Unsolubility and IR spectra are characterizing the compounds of the types MBr₃NCC(CN)₂ and RMNCC(CN)₂ as coordination polymers. IIb-metal derivatives form pyridine complexes [RMNCC(CN)₂(C₅H₅N)₂].     

Synthese und Eigenschaften von Metallocen‐ und Halbsandwich‐Komplexen mit pyridinhaltigen Brücken bzw. Seitenketten

Synthesis and Properties of Metallocene and Half Sandwich Complexes with Pyridine‐containing Bridges or Side Chains 2,6‐Bis(chlormethyl)pyridine ( 1 ) reacts with 4 equivalents of indenyllithium with formation of 2,6bis(methylenindenyl)pyridine‐dilitihium ( 2 ) from which with MCl₄ · 2 thf (M = Zr, Hf) the corresponding metallocene dichlorides 3 and 4 can be obtained. At reaction of 1 with 2 equivalents of C₅H₅Na only one Cl atom is replaced by a C₅H₅Na unit. Following reactions with indenyl lithium and ZrCl₄ · 2 thf give the unsymmetric complex [C₅H₃N–2,6‐CH₂‐(2‐C₅H₄)–(6‐C₉H₆)ZrCl₂] ( 7 ). – Picolylcyclopentadiene ( 8 ) and 1‐(picolyl)‐indene ( 9 ) are synthesized from 2‐chlomethyl‐pyridinium chloride and C₅H₅Na or indenyl lithium respectively, which are transferred in the half sandwich complexes (C₅H₄N–CH₂C₅H₄)MCl₃ (M = Ti 10 , Zr 11 ) and (C₅H₄–CH₂C₉H₆)ZrCl₃ ( 12) . The compounds were characterized by elemental analysis, ¹H n.m.r., ms, ir, and raman spectra. N → M interactions are discussed.     

Ruthenium(II) complexes with triphenylphosphine or triphenylarsine and other monodentate ligands

Synthesis and studies on some five-coordinate ruthenium(II) complexes, viz. [Ru(MPh₃)(C₆H₅CHO)₂Cl₂] and [Ru(MPh₃)₂(CO)Cl₂] (where M = P or As) have been described. Reactions of [Ru(MPh3)(C₆H₅CHO)₂Cl₂] with N,N-dimethylformamide, dimethylsulphoxide and pyridine and of [Ru(MPh₃)₂(CO)Cl₂] with pyridine are described.     

Die thermische zersetzung von metallorganischen wolfram- und molybdänkomplexen des typs M(CO)nCl2L2

The thermal decomposition reactions of the M(CO)_nCl₂L₂ type complexes M: W, Mo; n: 2, 3; L: P(C₆H₅)₃, As(C₆H₅)₃, OP(C₆H₅)₃ were studied. It was found that the tricarbonyl complexes split off the CO groups in 2+1 mole ratio, and after that the L ligands in a multi-step reaction. The splitting-off of the CO ligands might be a one-step (OPph₃), or a two-step process (Pph₃) in the case of the dicarbonyl compounds. The following thermal stability order is given: W>Mo; Pph₃>Asph₃>OPph₃; dicarbonyl ≈ tricarbonyl (ph - C₆H₅).     

Zur Wechselwirkung einiger Übergangsmetallhalogenide mit o-Mercaptophenol

The interaction of some transition metal halides with o-mercaptophenol o-Mercaptophenol reacts with WCl₆, TiCl₄, ZrCl₄, NbCl₅ and TaCl₅ giving the corresponding tris-chelat-komplexe W(C₆H₄OS)₃, H₂[M(C₆H₄OS)₃] (M = Ti, Zr), H[M(C₆H₄OS)₃] (M = Nb, Ta). (C₅H₅)₂TiCl₂ and (C₅H₅)₂ZrBr₂give in presence of triethylamine the compounds (C₅H₅)₂M(C₆H₄OS) (M = Ti, Zr). By reaction of nickel(II) acetyl-acetonate with o-mercaptophenol the polymeric octahedral complex nickel-bis-(o-hydroxy-thiophenolate) results.     

Über Pentafluorphenylthio-Metallkomplexe

The compounds M(CO)₅ · THF (M = Cr, Mo, W) react with sodium mercaptide, NaSR (R = C₆F₅, C₆H₅, C₂H₅), to give the mercapto-pentacarbonylmetallate anions [M(CO)₅ · · SR]^?. The preparation of some pentafluorophenylthio complexes, e. g. [(C₆H₅)₃P]₂MSC₆F₅(M = Cu, Ag, Au), [(C₆H₅)₃P]₂Hg(SC₆F₅)₂, is reported.     

Über Chalkogenolate. LIV. Untersuchungen über Thioameisensäuren 2. Darstellung und Eigenschaften von Dithioformiaten

K[HCS₂] was prepared by interaction of chloroform with K₂S. Rb[HCS₂] and Cs[HCS₂] were formed by reaction of trimeric dithioformic acid with alcoholates (X-ray data see ?Inhaltsübersicht”?). The dithioformates T1[HCS₂], In[HCS₂]₃, and M[HCS₂]₂ with M = Pb, Zn, Cd, Hg, and M[HCS₂] with M = [(C₆H₅)₄P], [(C₆H₅)₄As], [(C₂H₅)₄N], (C₆H₅)₃Sn have been prepared. The prepared compounds are investigated by different methods.     

Proton affinities by reactant ion monitoring: Triphenyl group Va compounds

Proton affinities of a series of triphenyl Group Va compounds have been determined by bracketing using reactant ion monitoring: (C₆H₅)₃N = 904 ± 8 kJ mol^?1, (C₆H₅)₃P = 968 ± 5 kJ mol^?1, (C₆H₅)₃As = 904 ± 8 kJ mol^?1 and (C₆H₅)₃Sb = 846 ± 8 kJ mol^?1. The large difference in substituent effect of phenyl for hydrogen between As or P and N may result from overlap of the 2p orbitals of N with the sp² orbitals on the ring carbons and lack of overlap for P or As. Proton affinities of phenylalkylphosphine oxides are essentially the same, 904 ± 8 kJ mol^?1, independent of alkyl group.     

Optisch aktive übergangsmetall-komplexe LXIV. Neue optisch aktive Cp(CO)Fe-acyl-komplexe mit

The novel complexes CpFe(CO)(COR)P(C₆H₅)₂NR'R^* with Cp = C₅H₅,C₉H₇ (indenyl); R = CH₃, C₂H₅, CH(CH₃)₂, CH₂C₆H₅;R` = H, CH<sub>3</sub>, C<sub>2</sub>H<sub>5</sub>, CH<sub>2</sub>C<sub>6</sub>H<sub>5</sub> and R<sup>*</sup> = (S)-CH(CH<sub>3</sub>)(C<sub>6</sub>H<sub>5</sub>), have been synthesized by reaction of CpFe(CO)<sub>2</sub>R wiht P(C<sub>6</sub>H<sub>5</sub>)<sub>2</sub>NR`R^* and characterized analytically as well as spectroscopically. The pairs of diastereoisomers RS/SS have been separated by preparative liquid chromatography and fractional crystallization, respectively. The optically pure complexes (+)₄₃₆- und ()₄₃₆-CpFe(CO)(COR)P(C₆H₅)₂NR`R^* are configurationally stable at room temperature. At higher temperatures they equilibrate with CpFe(CO)₂R and epimerize with respect to the Fe configuration.     

Reactions of methyltris(triarylphosphine)cobalt : II. Rearrangement of triarylphosphine and oxidative additions of aryl halides

Solutions of [(C₆H₅)₃P]₃CoCH₃ (I) in C₆H₅Cl yield biphenyl, triphenylphosphine, methyldiphenylphosphine and diphenylphosphine. In 4-ClC₆H₄CH₃, 4-methylbiphenyl and 4,4′-bitolyl form as well. Solutions of I in C₆H₆, C₆D₆, C₆H₅CH₃, C₆H₅Br yield only triphenylphosphine and biphenyl, while in 4-FC₆H₄I 4,4′-difluorobiphenyl is formed but no biphenyl. The cobalt compound is recovered as (Ph₃P)_nCoX or as CoX₂ (XCl, Br, I, n = 3 or 2) from reactions with arylhalides. The results are rationalized in terms of the very strong tendency for I to undergo oxidative addition reactions.     

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.     

Phenylphosphonsäure-bis(methylamid) und seine Reaktionen mit Phosphor(III)-Halogeniden

Phenyl Phosphonic Bis(methylamide) and its Reactions with Phosphorus (III) Halides Preparation of phenyl phosphonic bis(methylamide), I , from phenyl phosphonic dichloride and methylamine is described. I is characterized by its nmr, mass, and vibration spectra and by its reactions with PCl₃, CH₃PCl₂, and C₆H₅PCl₂. The two reactions mentioned last yield C₆H₅P(O)[N(CH₃)P(CH₃)Cl]₂ ( IIIa ) and C₆H₅P(O)[N(CH₃)P(C₆H₅)Cl]₂ ( IIIb ), respectively.     

Reactions of iridium and platinum complexes with N-sulfinyl compounds

The reactions of substituted N-sulfinylanilines with the complexes {Pt[P(C₆H₅₃]₂O₂} and {IrClCO[P(C₆H₅)₃]₂} have been reinvestigated. The former complex yields {Pt[P(C₆H₅)₃]₂SO₄} as the only isolable product in reactions with N-sulfinylaniline. In contrast to a previous report, Vaska's complex has been found not to react with C₆H₅NSO under anhydrous conditions. {Pt[P(C₆H₅)₃]₂-(C₂H₄)} reacts with N-sulfinyl compounds to give complexes of formula {Pt[P(C₆H₅)₃]₂-(RNSO)} where R = C₆H₅, p-O₂NC₆H₄, p-CH₃C₆H₄, or p-CH₃C₆H₄SO₂. {Pt[P(C₆H₅)₃]₃} reacts with C₆H₅NSO to give the same product obtained from reaction with the ethylene complex. Vaska's complex and its bromo analog form 1:1 adducts with p-O₂NC₆H₄NSO.     

Kinetic investigations of the Oxidative Addition Reactions of Simple Molecules with Carbon-Carbon Multiple Bonds to {Ir(CO)XL2}-type complexes

The kinetics of the addition reactions of tetracyanoethylene (TCNE), dimethyl maleate (DMM), diethyl maleate (DEM), maleicanhydride (MA), acetylenedicarboxylic acid (ADCA) and dimethyl acetylenedicarboxylate (DMADC) to complexes of the type trans-{Ir(CO)XL₂} (X = Cl, Br, I; L = P(C₆H₅)₃, P(p-CH₃C₆H₄)₃, P(p-CH₃OC₆H₄)₃, P(OC₆H₅)₃) in various solvents were investigated employing stopped-flow techniques. The kinetics were found to obey a second order/first order rate law for a reversible process. The rate constants obtained are discussed in terms of a Lewis acid-base model.     

Triallylborane and some its analogs as ligands in transition metal π-complexes: theoretical investigations

The structure, stability, and potential existence of chromium complexes with triallylborane B(CH₂—CH=CH₂)₃ and its analogs with coordination of the Cr atom to three double bonds are discussed. Complexes LCr(CO)₃ are studied where L = (C₃H₅)₃CH, (C₃H₅)₃B, (C₃H₅)₃BNMe₃, [(C₃H₅)₃BF]−, (C₂H₄)₃, C₆H₆, (C₃H₅)₃CPh, (C₃H₅)₃B(NC₅H₅). The calculations are carried out in DFT terms in approximations PBE/3z and BP86/TZ2P. The calculated dissociation energies of the studied complexes into the fragments Cr(CO)₃ and L range from 48.3 to 63.0 kcal mol⁻¹ (BP86/TZ2P) and from 54.2 to 66.9 kcal mol⁻¹ (PBE/3z). Ligands (C₃H₅)₃ER (ER = CPh, B(NC₅H₅)) can form two isomeric complexes A and B due to coordination of tricarbonylchromium to either three double bonds or benzene or pyridine ring. In the former case, isomer A is less stable as compared to isomer B, while in the latter case isomer Ais more stable. The possibility of selective synthesis of one of these isomers, namely, tris(η²-allyl)pyridineborane complex, is predicted.