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.     

Silicium-stickstoff-fluorverbidungen: V. Darstellung neuer silylaminofluorsilane

Compounds of the composition RR′SiFNR″Si(CH₃)₃ (R = H, F, CH₃, C₂H₅, C₃H₇, C₂H₃, C₆H₅, C(CH₃)₃; R = F, CH₃, C₆H₅; R″ = CH₃, C(CH₃)₃, Si(CH₃)₃) are obtained by the reaction of silicontetrafluoride or organo-substituted silicon-fluorides with the lithium salts of alkylsilylamines in a molar ratio of $\text{1}\text{1}$. The disubstituted compounds RSiF(NR′Si(CH₃)₃)₂ (R = H, F, CH₃, C₂H₃, C₆H₅; R′ = CH₃, C(CH₃)₃) result when the reactants are in a $\text{1}\text{2}$ molar-ratio. Likewise the unsymmetrical siliconfluorsilylamines of the formulae F₂Si(NRSi(CH₃)₃) (NR′Si(CH₃)₃) (R = CH₃, R′ = C(CH₃)₃), as well as the trisubstituted compounds FSi(NCH₃Si(CH₃)₃)₃ and FSi(NCH₃Si(CH₃)₃)₂(N(Si(CH₃)₃)₂) were made. By reacting phenyltrifluorsilane with dialkylamines ($\text{1}\text{2}$) C₆H₅SiF₂NR₂(R = CH₃, C₂H₅) was obtained. The IR-, mass-, ¹H and ¹⁹F NMR spectra of the above-mentioned compounds are reported.     

Darstellung neuer Alkylaminofluorsilane

Preparation of New Alkylaminofluorosilanes Aminofluorosilanes of the composition RSiF₂NR′R″ (R = H, CH₃, C₂H₃, C₆H₅; R′ = Si(CH₃)₃; R″ = C(CH₃)₃; R′ = R″ = i-C₃H₇), as well as C₆H₅SiF₂N[C(CH₃)₂CH₂]₂CH₂ are obtained by the reaction of fluorosilanes with the lithium salts of the corresponding amines in a molar ratio 1:1. The further reaction of these compounds with the lithium salts of alkylamines and anilin leads to the formation of the diaminofluorosilanes RSiFNR′R″NHR? (R? = C(CH₃)₃, i-C₃H₇, C₆H₅). The ¹H, ¹⁹F, ²⁹Si n.m.r. and mass spectra of the above mentioned compounds are reported.     

Spektroskopische Untersuchungen an Siliciumverbindungen. XXXI. Schwingungsverhalten von p-substituierten N,N-Bistrimethylsilylanilinen

The following p-substituted N,N-bis-trimethlsilyl anilines p-X? C₆H₄? N[Si(CH₃)₃]₂ are prepared by silylation of free amines: X = H, CH₃, C₂H₅, CH₃O, CH₃CO, F, Cl, Br, J, CN, C₆H_S, (CH₃)₃SiO, and [(CH₃)₃Si]₂N, and the isotopic derivatives C₆H₅? ¹⁵N[Si(CH₃)₃]₂ and C₆D₅N[Si(CH₃)₃]₂. The vibrational spectra are reported and assigned. The molecular symmetry of p-[(CH₃)₃Si]₂N? C₆H₄? N[Si(CH₃)₃]₂ is determined. The influence of the mass of the substituents X on the positions of the ν_sSiNSi vibrational frequencies is discussed.     

Unterschiedliche Cyclisierungsmechanismen von Aminofluorsilanen

Different Mechanisms of the Cyclisation of Aminofluorosilanes The reaction of aminofluorosilanes of the type RR′SiFNHR″ (R = H, F, CH₃, C₂H₃, C₆H₅, C(CH₃)₃; R′ = C(CH₃)₃, NiC₃H₇Si(CH₃)₃, NC(CH₃)₃Si(CH₃)₃, N[Si(CH₃)₃]₂; R″ = iC₃H₇, C(CH₃)₃, C₆H₅) with butyllithium depends on the steric influence of the ligands. With increasing size of the ligands the reaction takes its pathway from the substitution under LiF elimination via dimerisation with additional elimination of butan to the C? H cleavage and cyclisation via a methylen group. A further increase of the size of the substituted groups leads through the intermediate formation of a silicenium-ylid to ring closure reactions. These occure by migration of a methanid ion leading to intermolecular nucleophilic substitution. The isolated acyclic and heterocyclic compounds are described and the mass and ¹H-n.m.r. spectra are reported.     

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.     

Diphenyl-bis(P-trimethylphosphinimino)-phosphoniumchlorid

Diphenyl-bis(P-trimethylphosphinimino)-phosphonium Chloride The reaction of Na⊕(CH₃)₃Si? N? P(C₆H₅)₂? N? Si(CH₃)₃? III with (CH₃)₃PCI₂ results in the elimination of NaCI and (CH₃)₃SiCI and the formation of (CH₃)₃P = N? P(C₆H₅)₂? N = P(CH₃)₃ ⊕CI? VII . The mechanism of the reaction is discussed. (CH₃)₃P = N? P(C₆H₅)₂ = N? Si(CH₃)₃ V can be obtained as an intermediate. This intermediate, when synthesized by an other independent route, is found to react with (CH₃)₃PCI₂ to give the same product VII .     

X-ray analysis of 1,3-dioxa-6-aza-2-silacyclooctane derivatives

X-ray analysis has been conducted on four dioxaazasilacyclooctanes R₂Si(OCH₂CH₂)₂NR′ with R = C₆H₅, R′ = CH₃ (IV); R = C₆H₅, R′ = (CH₃)₃C (V); R = CH₃, R′ = C₆H₅ (VI) and R = R′ = C₆H₅ (VII). The interatomic distances SiN measured for these compounds had the values: 2.68 (IV), 3.16 (V), 3.19 (VI) and 3.08 Å (VII), indicating weak nitrogen—silicon interaction and a virtual lack of coordinate Si ← N bonding. The data of other authors and our own evidence suggest that the Si ← N interaction in these compounds is strongly influenced by the electronic effects of Si- and N-substituents and, in particular, by the steric effects of the latter.     

ÜBER EINIGE REAKTIONEN DER DIALKYLBENZYLPHOSPHINIMIDE

Abstract

Dialkylbenzylphosphine imides C₆H₅CH₂–PRR′[dbnd]N″ (R, R′ = CH₃, C₂H₅; R″ = H, CH₃, Si(CH₃)₃ react with aliphatic and aromatic aldehydes in benzene solution on heating to 80°C directly and in high yields according to a Horner-Wittig-reaction with formation of an olefine whereas ketones like benzophenone and acetophenone only perform an O/NR″ exchange (R″ = H).

Dialkylbenzylphosphinimide C₆H₅CH₂–PRR′[dbnd]N″ mit R, R′ = CH₃, C₂H₅ und R″ = H, CH₃, Si(CH₃)₃ reagieren mit aliphatischen und aromatischen Aldehyden in benzolischer Lösung beim Erwärmen auf 80°C direkt und mit hohen Ausbeuten im Sinne einer Horner-Wittig-Reaktion unter Olefinbildung, während sich mit Ketonen wie Benzophenon oder Acetophenon nur ein O/NR″-Austausch (R″ = H) vollzieht.     

Alkoxylierung von bis(trimethylsilyl)-aminofluorsilanen,sowie siloxanbildung unter äthereliminierung

The reaction of bis(trimethylsilyl)aminofluorsilanes, (Me₃Si)₂NSiF₂R (R = CH₃ or F), with sodium alcoholates or sodium phenylate yields under elimination of NaF alkoxy- and aryloxy-aminofluorosilanes of the composition (Me₃Si)₂NSiF(R)OR′(R′ = CH₃, C₂H₅, C₃H₇, C₆H₅). A disiloxane is formed by thermal elimination of diethyl ether from bis(trimethylsilyl)aminomethylfluoroethoxysilane. The IR, mass, ¹H and ¹⁹F NMR spectra of the above-mentioned compounds are reported. ab]Die Reaktion von Bis(trimethylsilyl)-aminofluorsilanen des Typs (Me₃Si)₂NSiF₂R (R = F, CH₃) mit Natriumalkoholaten und Natriumphenolat führt unter NaF-Abspaltung zu Alkyl- und Aryloxyaminofluorsilanen der Zusammensetzung: (Me₃Si)₂NSiF(R)OR′ (R′ = CH₃, C₂H₇, C₆H₅, C₆H₅). Ein Disiloxan könnte durch die thermische Eliminierung von Diäthyläther aus Bis(trimethylsilyl)aminomethyl-fluor-äthoxy-silylarnin erhalten werden.Die IR-, Massen-, ¹H- und ¹⁹F-NMR-Spektren der dargestellten Verbindungen werden mitgeteilt.     

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.     

Triorganoantimon- und Triorganobismutderivate von 2-Pyridincarbonsäure und 2-Pyridylessigsäure Kristall- und Molekülstrukturen von (C6H5)3Sb(O2C-2-C5H4N)2 und (CH3)3Sb(O2CCH2-2-C5H4N)2

Triorganoantimony and Triorganobismuth Derivatives of 2-Pyridinecarboxylic Acid and 2-Pyridylacetic Acid. Crystal and Molecular Structures of (C₆H₅)₃Sb(O₂C-2-C₅H₄N)₂ and (CH₃)₃Sb(O₂CCH₂-2-C₅H₄N)₂ Triorganoantimony and triorganobismuth dicarboxylates R₃M(O₂C-2-C₅H₄N)₂ (M = Sb, R = CH₃, C₆H₅, 4-CH₃OC₆H₄; M = Bi, R = C₆H₅, 4-CH₃C₆H₄) and (CH₃)₃Sb(O₂CCH₂-2-C₅H₄N)₂ have been prepared from (CH₃)₃Sb(OH)₂, R₃SbO (R = C₆H₅, 4-CH₃OC₆H₄), or R₃BiCO₃ (R = C₆H₅, 4-CH₃C₆H₄) and the appropriate heterocyclic carboxylic acid. Vibrational spectroscopic data indicate a trigonal bipyramidal environment of M the O(? C)-atoms of the carboxylate ligands being in the apical and three C atoms (of R) in the equatorial positions; in addition coordinative interaction occurs in the 2-pyridinecarboxylates between M and O(?C) of one and N of the other carboxylate ligand and in (CH₃)₃)Sb(O₂CCH₂-2-C₅H₄N)₂ between Sb and O(?C) of both carboxylate ligands. (C₆H₅)₃Sb(O₂C-2-C₅H₄N)₂/(CH₃)₃Sb(O₂CCH₂-2-C₅H₄N)₂ crystallize monoclinic [space group P2₁/c/P2₁/n; a = 892.6(9)/1043.4(6), b = 1326.9(6)/3166.2(18), c = 2233.1(9)/1147.5(7) pm, β = 99.74(8)°/97.67(5)° Z = 4/8; d(calc.) = 1.522/1.553 × Mg m^?3; V_cell = 2606.7 × 10⁶/3757.0 × 10⁶pm³, structure determination from 3798/4965 independent reflexions (F ≥ 4.0 σ(F))/(I ≥ 1.96 σ(I), R(unweighted) = 0.024/0.036]. Sb is bonding to three C₆H₅/CH₃ groups in the equatorial plane [mean distances Sb? C: 212.2(3)/208.7(6) pm] and two carboxylate ligands via O in the apical positions [Sb? O distances: 218.5(2), 209.9(2)/212.1(3), 213.2(3) pm]. In (C₆H₅)₃Sb(O₂C-2-C₅H₄N)₂ there is a short Sb? O(?C) and a short Sb? N contact [Sb? O: 272.1(2), Sb? N: 260.2(2) pm] and distoritions of the equatorial angles [C? Sb? C: 99.2(1)°, 158.2(1)°, 102.0(1).] and of the axial angle [O? Sb? O: 169.9(1)°], and in (CH₃)₃Sb(O₂CCH₂-2-C₅H₄N)₂, which contains two different molecules in the asym-metric unit, there are two Sb? O(?C) contacts [Sb? O, mean: 302.2(4), and 310.7(4)pm, respectively] and distortions of the equatorial angles [C? Sb? C: 114.5(2)°, 132.4(3)° 113.1(2)°, and 123.9(3)° 115.5(2)°, 120.6(3)°, respectively] and of the axial angles [O? Sb? O: 174,9(1)°, 177.9(1)°, respectively].     

Umsetzungen von Borazinderivaten mit Bis(trimethylsilyl)-acetamid und Lithiumhexamethyldisilazan

Bis-(trimethylsilyl)acetamide (BSA) reacts with borazines [RNBX]₃, R=H,X=F; R=CH₃,X=F; R=C₆H₅,X=F and R=C₆H₅,X=Cl to the corresponding borazines,X=OSi(CH₃)₃. The¹H-NMR signal of the Si(CH)₃-groups of [C₆H₅NBOSi(CH₃)₃]₃ is at abnormally high field. With [CH₃NBCl]₃,BSA forms borazines which contain both Si(CH₃)₃O- and O?C(CH₃)=NSiR₃ groups bonded to the boron atoms. With LiN[Si(CH₃)₃]₂, [CH₃NBCl]₃ forms silylaminoboranes.¹H-NMR, mass spectrometric and analytical data are reported.     

Synthese von Fluoro-λ5-monophosphazenen und Fluoro-1, 3-diaza-2λ5, 4λ5-diphosphetidinen mittels der Staudinger-Reaktion

Synthesis of Fluoro-λ⁵-monophosphazenes and Fluoro-1,3-diaza-2λ⁵,4λ⁵-diphosphetidines by Means of the Staudinger Reaction 35 Tetrafluoro- and 2 difluorodiaza-diphosphetidines as well as 4 difluoro- and 30 monofluoro-λ⁵-monophosphazenes were prepared by the Staudinger reaction between tervalent phosphorus fluorides, R_nPF_3?n (n = 1, 2; R = R₂N, (CH₂)₅N, O(CH₂)₄N, RO, (CH₂O)₂, alkyl, aryl) and phenylazides, X? C₆H₄N₃ (X = H, 4-CH₃, 4-Cl, 4-Br, 4-NO₂, 3-NO₂). PF₃ does not react with phenylazide The influence of substituents on the structure of the reaction products is discussed. Kinetic measurements allowed to determine the constants λ^P_I of the substituents (CH₂)₅N, O(CH₂)₄N and R(C₆H₅)N (R = CH₃, C₂H₅, n-C₄H₉).     

Cyclisierung neuer Trimethylsilylalkylaminohalogensilane

Cyclisation of New Trimethylsilylalkylaminohalosilanes Compounds of the composition RSiCl₂NR′SiMe₃ (R = Cl, CH₃, C₂H₅, C₆H₅; R′ = CH₃, C₂H₅, C(CH₃)₃) are obtained by the reaction of silicon halides with the lithium salts of silylamines. Under suitable experimental conditions the reaction leads to the formation of the corresponding Si? N four- and six-membered ring systems (RSiHalNR′)_n (Hal = F, Cl; n = 2 or 3) under elimination of trimethylhalosilane. The i.r., mass, ³⁵Cl-n.q.r., ¹H and ¹⁹F-n.m.r. spectra of these compounds are reported.     

Bildung siliciumorganischer Verbindungen. 66. (H2Si?CH2)2 und Si-substituierte Derivate

Formation of Organosilicon Compounds. 66. (H₂Si? CH₂)₂ and Si-substituted Derivatives (H₂Si? CH₂)₂ 1 is formed in the reaction of (Cl₂Si? CH₂)₂ with LiAlH₄. In 1 , the halogenation of the SiH bond is so much preferred compared to the ring cleavage reaction, that 1 reacts with Cl₂ or Br₂ to form successively all compounds form 1-monochlor-1,3-disilacyclobutane to (X₂Si? CH₂)₂ (X = Cl, Br). The stability of the 1,3-disilacyclobutane skeleton towards HBr or Br₂ increases as the electronegativity of the Si-substituents increases. Thus, (Cl₂Si? CH₂)₂ is cleaved neither by HBr nor by Br₂, whereas e. g. [H(C₆H₅)Si? CH₂]₂ reacts to [Br(C₆H₅)Si? CH₂]₂ with Br₂, but yields meH(C₆H₅)Si? CH₂? SiBr(C₆H₅)H (me = CH₃) with HBr. In [me(C₆H₅)Si? CH₂]₂, the four-membered ring is cleaved by Br₂ as well as by HBr. The ¹H-, ²⁹Si- and ¹³C-n.m.r. data are reported.     

Zur Bildung von Disilylphosphino-Element-Verbindungen des C,Si, P

The Formation of Disilylphosphino-Element Compounds of C, Si, P The reactions of (me₃Si)₂PLi · OR₂ a (OR₂ = 1 monoglyme or 2 THF; me = CH₃) with CH₃Cl, CH₂Cl₂, ClCH₂CH₂Cl and ClCH₂? C₆H₅ give the compounds (me₃Si)₂Pme, (me₃Si)₂P? CH₂? P(Sime₃)₂, (me₃Si)₂P? CH₂CH₂Cl, (me₃Si)₂P? CH₂CH₂? P(Sime₃)₂ and (me₃Si)₂P? CH₂C₆H₅ respectively. In the same manner a reacts with me₂SiCl₂ in a molar ratio 1:1 to (me₃Si)₂P? Sime₂Cl and in a molar ratio 2:1 to (me₃Si)₂P? Sime₂? P(Sime₃)₂ b . The compound b decomposes to [me₃SiP? Sime₂]₂ and (me₃Si)₃P at 220°C. In the reactions of a with ClP(C₆H₅)₂ and ClPme₂ the compounds (me₃Si)₂P? P(C₆H₅)₂ and (me₃Si)₂P? Pme₂, respectively, are obtained. a reacts with HgCl₂ to (me₃Si)₂P? P(Sime₃)₂. (me₃Si)₃P can be cleaved with ClP(C₆H₅)₂ and ClPme₂ yielding (me₃Si)₂P? P(C₆H₅)₂ and (me₃Si)₂P? Pme₂, respectively. The ¹H- and ³¹P-n.m.r. and mass spectroscopic data are reported.     

Synthesis reactivity and electrochemical properties of substituted cyclopentadienyl cobalt (III) complexes

Cyclopentadienyl cobalt complexes (η⁵‐C₅H₄R) CoLI₂ [L = CO,R=‐COOCH₂CH=CH₂ (3); L=PPh₃, R=‐COOCH₂‐CH=CH₂ (6); L=P(p‐C₆H₄O₃)₃, R = ‐COOC(CH₃) = CH₂ (7), ‐COOCH₂C₆H₅ (8), ‐COOCH₂CH = CH₂ (9)] were prepared and characterized by elemental analyses, ¹H NMR, ER and UV‐vis spectra. The reaction of complexes (η⁵‐C₅H₄R)CoLI₂ [L= CO, R= ‐COOC(CH₃) = CH₂ (1), ‐COOCH₂C₆H₅(2); L=PPh₃, R=‐COOC (CH₃) = CH₂ (4), ‐COOCH₂C₆H₅ (5)] with Na‐Hg resulted in the formation of their corresponding substituted cobaltocene (η⁵‐C₅H₄R)₂ Co[R=‐COOC(CH₃) = CH₂ (10), ‐COOCH₂C₆H₅ (11)]. The electrochemical properties of these complexes 1–11 were studied by cyclic voltammetry. It was found that as the ligand (L) of the cobalt (III) complexes changing from CO to PPh₃ and P(p‐tolyl)₃, their oxidation potentials increased gradually. The cyclic voltammetry of α,α′‐substituted cobaltocene showed reversible oxidation of one electron process.     

Trivalent-pentavalente Phosphorverbindungen/Phosphazene. V. Darstellung,Eigenschaften und Reaktionen neuer Phosphonig- und Phosphinigsäureester

Trivalent-Pentavalent Phosphorus Compounds/Phosphazenes. V. Preparation, Properties, and Reactions of New Phosphonous- and Phosphinous Acid Esters Phosphonous diesters R? P(OR′)₂ (R ? CH₃, Ph and R′ ? CH₂? CF₃) have been synthetized by reaction of phosphonous dichlorides with 2, 2, 2-trifluoroethanol in the presence of a base. These diesters react with trimethyl(trimethylsilylimino)phosphorane, (CH₃)₃P?N? Si(CH₃)₃ by desilylation and N? P-linking to phosphinous acid esters (CH₃)₃P?N? P(OR′)R. The phosphinous acid esters react with methyl iodide to the quaternary salts [(CH₃)₃P? N? P(OR′)(R)CH₃]⁺I^?. The compounds are characterized by elementary analysis and spectroscopical methods.     

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 .