μ-Oxo-bis(triorganoantimon- und -bismutsulfonate). Kristallstruktur von {(CH3)3SbOH2]2}O3SC6H5)2

μ-Oxo-bis(triorganoantimony- and -bismuthsulfonates) (R₃MO₃Sr′)₂O[M  Sb, R  Ph, benzyl, M  Bi, R  Ph; R′  Me, CH₂CH₂OH, CF₃, Ph, 4-CH₃C₆H₄, 2,4-(NO₂)₂C₆H₃] and (Me₃SbO₃SR′)₂O · nH₂O (n  2, R′  CF₃, Ph, 4-CH₃C₆H₄; n  0, R′  CH₃, CH₂CH₂OH) have been prepared by reaction of (Ph₃SbO)₂ and Me₃Sb(OH)₂, respectively, with appropriate sulfonic acids or with (R₃MX)₂O (R  Ph, benzyl; X  Br) and R′SO₃H in the presence of Ag₂O. The anhydrous compounds (Me₃SbO₃SR′)₂O are obtained by heating the hydrates. Me₃Sb(OH)₂ and 2,4-(NO₂)₂C₆H₃SO₃H react to give the hydroxosulfonate Me₃Sb(OH)O₃SR′. CH₃OH solvolyzes the products. A covalent structure, with pentacoordinated Sb or Bi atoms, unidentate O₃SR′ ligands and μ-oxygen in apical, and R in equatorial positions, is inferred from the vibrational data for all nonhydrated sulfonate compounds. A correlation between ν_as(SbOSb) vibration and SbOSb bond angles in hexaphenyl distiboxans was established, which indicates that the SbOSb bridges are linear in (Ph₃SbO₃SR′)₂O (R′  2,4-(NO₂)₂C₆H₃, 2,4,6-(NO₂)₃C₆H₂) and bent in the other compounds. Data also indicate that there is a linear BiOBi bridge in (Ph₃BiO₃SCH₂CH₂OH)₂O. The hydrated compounds have a distinctly different ionic structure one H₂O being coordinated apically to each of the pentacoordinated Sb atoms in the cation [(Me₂SbOH₂)₂O]²⁺. This proposal is verified by the crystal structure determination of (Me₃SbO₃SPh)₂O · 2H₂O which revealed an ionic structure: [(Me₃SbOH₂)₂O](O₃SPh)₂. The angles μ-OSbO(H₂O) of 171.7(2) and 171.0(2)° and μ-OSbC(CH₃) of 98.3° (mean) reflect the distortion of the trigonal bipyramidal surrounding of the Sb atoms, and the long SbO(H₂O) distance of 244.4(5) pm (mean) the rather weak bonding of the water molecules to Sb. The distances S [144.6(6) pm (mean)] and the angles OSO [112.6(4)° (mean)] in the sulfonate anion are essentially identical. Hydrogen bonds exist between the water ligands and O atoms of the anions.     

Trivalent-pentavalente Phosphorverbindungen/Phosphazene. IV. Darstellung und Eigenschaften neuer N-silylierter Diphosphazene

Trivalent-Pentavalent Phosphorus Compounds/Phosphazenes. IV. Preparation and Properties of New N-silylated Diphosphazenes Phosphazeno-phosphanes, R₃P = N? P(OR′) ₂ (R = CH₃, N(CH₃)₂; R′ = CH₂? CF₃) react with trimethylazido silane to give N-silylated diphosphazenes, R₃P = N? P(OR′)₂ = N? Si(CH₃)₃ compounds decompose by atmospherical air to phosphazeno-phosphonamidic acid esters, R₃ P?N? P(O)(O? CH₂? CF₃)(NH₂). Thermolysis of diphosphazene R₃P = N? P(OR′) ₂ = N? Si(CH₃)₃ (R = CH₃, R′ = CH₂? CF₃) produces phosphazenyl-phosphazenes [N?P(N?P(CH₃)₃)OR′] _n. The compounds are characterized by elementary analysis, IR-, ¹H_-, ²⁹Si-, ³¹P-n.m.r., and mass spectroscopy.     

Basische metalle : XXXVI. Die synthese stabiler hydrido(olefin)rhodium-komplexe und von[C5H5Rh(PMe3)(η3-CH3CHC6H5)]PF6

The complexes C₅H₅Rh(PMe₃)C₂H₃R′ (R′  H, Me, Ph) and C₅H₅Rh(PR₃)C₂H₄(PR₃  PMe₂Ph, PPrⁱ₃) are prepared by reaction of[PMe₃(C₂H₃R/t')RhCl]₂ or [PR₃(C₂H₄)RhCl]₂ and TlC₅H₅, respectively. They react with HBF₄ in ether/propionic anhydride to form the BF₄ salts of the hydrido(olefin)rhodium cations [C₅H₅RhH(C₂H₃R′)PR₃]⁺(R  Me; R′  H, Me and R  Prⁱ; R′  H). From C₅H₅Rh(PMe₃)C₂H₃Ph and CF₃COOH/NH₄PF₆ the η³-benzyl complex [C₅H₅Rh(PMe₃)(η³-CH₃CHC₆H₅)]PF₆ is obtained. The reversibility of the protonation reactions is demonstrated by temperature-dependent NMR spectra and by deuteration experiments. The complexes C₅H₅Rh(PMe₃)C₂H₃R′ (R′  H, Ph) and C₅H₅Rh(PMe₂Ph)C₂H₄ react with CH₃I in ether to give the salts [C₅H₅RhCH₃(C₂H₃R′)PR₃]I which in THF or CH₃NO₂ yield the neutral compounds C₅H₅RhCH₃(PR₃)I.     

The behaviour of beryllium μ4-oxo-μ-carboxylates under electron impact

The electron impact mass spectra of eight polynuclear beryllium complexes Be₄O(RCO₂)₆ (R?H, CH₃, C₂H₅) and Be₄O(RCO₂)₅OR′ (R?CH₃, R′?H, CH₃, C₂H₅, C₃H₇; R?C₂H₅, R′?C₂H₅) are reported. The major fragmentations involve the elimination of (RCO)₂O (RCOOR′) or Be(RCO₂)₂ (Be(RCO₂)OR′) from the ions [M? L]⁺ and of {(R? H)CO}, (R′? H), H₂O and BeO from the lighter ions. The fragmentation patterns are practically independent of the organic groups present and can be rationalized by stereochemical considerations.     

New molybdenocene dihydrocarbyls

The preparation and characterization of [Mo(η⁵-C₅H₅)₂R₂)] (R  C₂H₅, ⁿC₄H₉,C₆H₅) and [Mo(η⁵-C₅H₅)₂R₂] PF₆ (R  C₂H₅, ⁿC₄H₉) are described. Cyclic voltammograms in CH₃CN and CH₂Cl₂ show that the reversible 1-electron oxidation of [Mo(η⁵-C₅H₅)₂R₂] (R  C₂H₅, ⁿC₄H₉) occurs at higher potentials (ca. −210 mV) than that for [Mo(η⁵-C₅H₅)₂(CH₃)₂] (ca. −270 mV).     

Formation of organometallic compounds of carbene and carbine types by the interaction of RLi with neodymium and yttrium chlorides in various media

It has been established that in the interaction of NdCl₃ and YCl₃ with RLi, where R  CH₂C₆H₅, CH₂C(CH₃)₂C₆H₅, CH₂Si(CH₃)₃, unusual organometallic compounds are formed. They are stable in hydrocarbon solutions. The benzyl and neophyl derivatives are carbene type complexes containing one R group at a trivalent metal atom. In all cases the reaction is accompanied by the evolution of RH as the main product and some stilbene and tolan when R  CH₂C₆H₅. The mechanism of this reaction is discussed.     

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.     

Darstellung und Eigenschaften von Diorganyl-bis(seleninato-O,O′)-Komplexen des Bleis und Zinns

Preparation and Properties of Diorganyl-bis(seleninato-O,O′) Complexes of Lead and Tin The colourless, thermically stable diorganyl-bis(seleninato-O , O ′) complexes of lead and tin R₂E(O₂SeR′)₂[E = Pb (1) , Sn (2) ] are obtained by reaction of diorganyllead- and -tindichlorides R₂ECl₂ (R = C₆H₅, CH₃, C₂H₅, n-C₄H₉) with different sodiumseleninates R′SeO₂Na (R′ = C₆H₅, CH₃, C₂H₅) at 20°C. On the basis of their i.r., Raman, and Mößbauer spectra and their slightly solubility in all organic solvents a polymeric structure is supposed in which each two R′SeO₂ - ligands are linking two lead and tin atoms respectively (c.n. = 6) intermolecular (seleninato-O , O ′). The organic residues are in trans-position.     

Darstellung und eigenschaften von diorganogermaniumdisulfinsäureestern

Diorganogermaniumdisulfinic esters of the type R₂Ge(O₂SR′)₂ (R = CH₃, R′ = CH₃, C₆H₅, p-CH₃C₆H₄; R = C₆H₅, R′ = CH₃, p-CH₃C₆H₄) which are sensitive to hydrolysis are obtained by reaction of the corresponding diorganogermanium dichlorides with anhydrous silver sulfinates. The newly prepared compounds are thoroughly investigated on the basis of their ¹H NMR, mass, IR and Raman spectra. The methyl ester (CH₃)₂Ge(O₂SCH₃)₂ is compared with the already known sulfinato complex of tin with the same formal composition.     

Massenspektrometrische Untersuchungen an Organophosphorverbindungen. II—Elektronenstoßinduzierte Fragmentierungen von Tetraorganodiphosphandisulfiden

The behaviour under electron impact (70 eV) which includes some rearrangement processes of some tetraorganodiphosphanedisulfides R₂P(S)-P(S)R₂ (R ? CH₃, C₂H₅, n-C₃H₇, n-C₄H₉, C₃H₅, C₆H₅) and CH₃RP(S)–P(S)CH₃R (R ? C₂H₅, n-C₃H₇, n-C₄H₉, C₆H₅, C₆H₅, C₆H₅,CH₂) is reported and discussed. Fragmentation patterns which are consistent with direct analysis of daughter ions and defocusing metastable spectra are given. The atomic composition of many of the fragment ions was determined by precise mass measurements. In contrast to compounds R₃P(S) loss of sulphur is not a common process here. The first step in the fragmentation of these compounds is cleavage of one P–C bond and loss of a substituent R?. The second step is elimination of RPS leading to [R₂PS]⁺ from which the base peaks in nearly all the spectra arise. The phenyl substituted compounds give spectra with very abundant [(C₆H₅)₃P]^+. and [(C₆H₅)₂CH₃P]^+. ions respectively, resulting from [M]^+. by migration of C₆H₅. Rearrangement of [M]^+. to a 4-membered P-S ring system prior to fragmentation is suggested.     

A novel synthesis of carbene complexes of manganese and molybdenum containing the trichlorogermyl group

A number of carbene complexes of formulas Cl₃GeMn(CO)₄C(OR′)R and C₅H₅Mo(CO)₂(GeCl₃)C(OR′)CH₃ (R = CH₃, C₆H₅; R′ = CH₃, C₂H₅) have been prepared by the reaction of [N(C₂H₅)₄]GeCl₃ with CH₃Mn(CO)₅, C₆H₅Mn(CO)₅, or C₅H₅Mo(CO)₃CH₃ followed by alkylation of the resulting trichlorogermylacylcarbonylmetallate ion. The compound C₅H₅Mo(CO)₂(GeCl₃)$\text{COCH}{}_2\text{CH}{}_2\text{C}$H₂ has been prepared directly by the reaction of [N(C₂H₅)₄]GeCl₃ with C₅H₅Mo(CO)₃(CH₂)₃Br.     

An ESR study of some group IVB free radical adducts of diethylketomalonate

The formation of the compound RSnX(acac)₂ (acac = 2,4-pentanedionato) by reaction of bis(2,4-pentanedionato)tin(II) on a halide RX with R = CH₃, C₂H₅, C₄H₉, C₆H₅, CH₂I, (C₆H₅)₃SnCH₂, (C₂H₅)₃SnCH₂ and X = I, Br has been studied by polarography. At 25°C, it is in fact an equilibrium whose constant has been measured. The intermediate formation of the ion-pair [RSn(acac)₂⁺X^?] has allowed us to explain the experimental results.     

Disubstituted vinylidene complexes of iron and ruthenium: nucleophilic properties of ν1-acetylide ligands

The η¹-acetylide complexes (C₅H₅)ML₂(CCR) (M  Fe, Ru; L  PPh₃, L₂  Ph₂PCH₂CH₂PPh₂) are nucleophilic at the β-carbon and react with a variety of mild electrophiles to yield the corresponding disubstituted vinylidene complexes [(C₅H₅)ML₂ (CCR′) PF₆.     

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.     

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 .     

Darstellung von Tetracarbonyl-triphenylphosphinmanganorganoplumbanen R4−nPb[Mn(CO)4P(C6H5)3]n (RCH3, C6H5; n = 1,2)

Preparation of R_4?nPb[Mn(CO)₄P(C₆H₅)₃]_n Compounds (R?CH₃, C₆H₅; n = 1, 2) As the first examples of organolead manganese carbonyls substituted in the manganese carbonyl ligand compounds of the type R_4?nPb[Mn(CO)₄P(C₆H₅)₃]_n (R?CH₃, C₆H₅; n = 1, 2) have been prepared by the alkali salt method from R_4?nPbCl_n and NaMn(CO)₄P(C₆H₅)₃. (C₆H₅)₂Sn[Mn(CO)₄P(C₆H₅)₃]₂ has been gained by the same method and also by thermal ligand exchange. According the IR data the ligand P(C₆H₅)₃ is trans to the tetrahedrally surrounded lead. In solution to compounds are monomeric.     

Complexes carbeniques des ferroporphyrines: Preparation de complexes carbeniques comportant deux substituants electrodonneurs par alcoolyse ou thionolyse des complexes halogenocarbeniques correspondants

α-Halocarbeneporphyriniron complexes, Fe(P)(C(Cl)R) react with alcohols or thiols with substitution of the chlorine atom by OR′ or SR′ groups. This reaction has been used to obtain new carbeneporphyriniron complexes in which the carbene ligand is substituted by two electrodonating groups. The complexes Fe(P)(C(XR′)R) with XR′ = OCH₃ or OC₂H₅, R = CH₃ or (CH₃)₂CH and P = TPP (tetraphenylporphyrin) or TTP (tetratolylporphyrin) and with XR′ = SCH₂C₆H₅, R = CH₃ and P = TPP or TTP, have been isolated and fully characterized.     

Organische Phosphorverbindungen XXXVIII. Darstellung und Eigenschaften von Tris-(dialkoxyphosphonyl-methyl)-, Tris-(alkoxyphosphinyl-methyl)-und Tris-(oxophosphoranyl-methyl)-phosphinsäureestern sowie der entsprechenden Säuren [1]

Tris-chloromethyl-phosphine oxide, (ClCH₂₎₃ P?O(I), is obtained by chlorination of (HOCH₂₎₃P?O with PCl₅ or (C₆H₅₎₃PCl₂, and also by oxidation of (CICH₂₎₃P?O and (ClCh₂₎₂(CH₃)P?O. High yields of tris-(dialkyloxyphosphonly-methyl)-phosphine oxides, [RO₂(O)PCH_2]2P?O (II) (R?CH₃, C₂H₅, iso-C₃H₇, n-C₄H₉, 2- ethyl-hexyl), tris (alkyloxyphosphinyl-methyl)-phosphine oxides, [R₂(O)PCH_2]3P?O(R = C₆H₅, CH₃) are obtained by heating tris-chloromethyl-phosphine oxides, [(RO) (R′) (O)PCH_2]3P?O (R = C₄H₉, R′? C₆H₅) and tris-(oxophosphoranyl-phosphine oxides with phosphites, phosphonites and phosphinites, respectively, at 170–180°C for several hours. Compounds II possess an extraordinarily high absorption capacity. Thus a warm. 2% solution of II (R = C₂H₅) in benzene solidifies completely on cooling so that no benzene can be poured off. Tris-dihydroxyphosphonyl-methyl)-phosphine oxide, [(HO)₂(O)PCH_2]3P?O, obtained by hydrolysis of II (R ? C₂H₅) with refluxing conc. HCl or by thermal decomposition of II (R ? iso-C₃H₇) at 190°, titrates in aqueous solution as a hexabasic acid with breaks at pH = 4,4 (three equivalents) and pH = 10,7 (three equivalents). It forms crystalline salts with amines, alkali and alkaline earth metals, and is an excellent chelating agent. The ¹H- and ^31?P-NMR. spectra of all the compounds prepared are discussed.     

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.     

S,N,N′-Substituted sulfurdiimines as ligands: II. Compounds [(ν3-RC3H4)Pd{R1NS(R2)NR1}] (R  H,CH3;R1  aryl; R2  CH3, t-C4H9) and some related triazenido and amidino compounds of palladium(II)

The complexes [(ν³-RC₃H₄)Pd{R¹NS(R²)NR¹}] (R  H, CH₃;R¹  aryl; R²  CH₃, t-C₄H₉) have been obtained from the reaction of [(ν³-RC₃H₄)PdCl]₂ with [Li{R¹NS(R²)NR¹}]; two isomers are produced, differing in the orientation of the allyl group. The sulfurdiimino group has some π-allylic character. The compounds decompose in solution into azo—arenes and [(ν³-RC₃H₄)Pd(SR²)]₂, and this is shown to be dependent upon steric and electronic factors.The properties of the sulfurdiimino compounds are compared with those of the compounds [(ν³-RC₃H₄)Pd(R³N₃R³)]₂ and [(ν³-RC₃H₄)Pd(R³NC(R⁴)NR³)]₂ (R  H, CH₃;R³  CH₃, aryl; R⁴  H, CH₃), which have been prepared by new methods.