Zur reaktion von metall-koordiniertem kohlenmonoxid mit yliden: XI. Einige neuartige η1-vinyl-komplexe des eisens durch deprotonierung kationischer carbenkomplexe mit trimethyl(methylen)phosphoran

Novel η¹-vinyl complexes of the type Cp(CO)(L)FeC(OMe)C(R)R′ (R = R′ = H, Me; R = H, R′ = Me; L = Me₃P, Ph₃P) are obtainied via methylation of the acyl complexes Cp(CO)(L)FeC(O)R (R = Me, Et, i-Pr) with MeOSO₂F and subsequent deprotonation of the resulting carbene complexes [Cp(CO)(L)FeC(OMe)R]SO₃F with the phosphorus ylide Me₃PCH₂. The same procedure can be applied for the synthesis of the pentamethylcyclopentadienyl derivative C₅Me₅(CO)(Me₃P)FeC(OMe)CH₂, while treatment of the hydroxy or siloxy carbene complexes [Cp(CO)(L)FeC(OR)Me]X (R = H, Me₃Si; X = SO₃CF₃) with Me₃CH₂ results in the transfer of the oxygen bound electrophile to the ylidic carbon. Some remarkable spectroscopic properties of the new complexes are reported.     

The preparation of functional alkylidynetricobalt nonacarbonyl complexes from dicobalt octacarbonyl

Various functionally-substituted methylidynetricobalt nonacarbonyl derivatives, RCCo₃(CO)₉, where R is D, Me₃Si, PhMe₂Si, (MeO)₂P(O), (EtO)₂P(O), Me₃COC(O), Me₃SiOC(O), Et₂NC(O), CH₃C(O), C₂H₅C(O), n-C₃H₇C(O), Me₂-CHC(O), n-C₄H₉C(O), Me₃C(O), PhC(O), p-CH₃C₆H₄C(O), p-BrC₆H₄C(O), HOCH₂, HC(O), CH₃O and Me₂N, have been prepared by reaction of dicobalt octacarbonyl with the appropriate RCX₃ or RCHX₂ (XCl or Br) compound.     

1-Alkoxy-2-azaallenyl-komplexe von chrom und wolfram

The successive reaction of (CO)₆M with Na[NCR₂¹] and [Et₃O]BF₄ yields (CO)₅M[C(NCR₂¹)OEt] (II: M = Cr; III: M = W; CR₂¹ = C(C₆H₄Br-p)₂ (a), CPh₂ (b), C(C₆H₄OMe-p)₂ (c), C(C₆H₄)₂O (d), CBu₂^tt (e)). Hexacarbonyltungsten, (CO)₆W, reacts with Na[NCPh₂] and MeOSO₂F to give (CO)₅W[C(NCPh₂) OMe] (IV). X-Ray analysis of IIe shows that: (1) the CNC fragment is almost linear (171.7°); (2) the two NC bond lengths are equal within experimental error; and (3) the O,C,Cr,N plane is perpendicular to the C(Me₃),C,N,C(Me₃) plane (90.0°). Therefore compounds II–IV are best described as 1-alkoxy-2-azaallenyl complexes.     

A dipole moment study of n-trimethyl-ammoniobenzamidates and n-benzoyliminodimethylsulphur(iv)

Analysis of the dipole moments of N-trimethylammoniobenzamidates Me₃N⁺-N^?COC₆H₄X, with X = H, p-F, p-Cl or p-NO₂, and of N-aroyliminodimethylsulphur(IV) Me₂SNCOC₆H₄X (X = H and p-NO₂) shows that, as solutes, these compounds exist in the syn conformation. Models are proposed for N-trimethylammonio-orthochloroben-zamidate and N-orthocyanobenzoyliminodimethylsulphur(IV). The (Me₃N⁺-N^t-) and (SN) dipole moments, and the (N-CO) and (SN-CO) mesomeric moments, are derived and discussed.     

Synthesen mit verbindungen R3M-Hg-MR3 und (R2M-Hg)n(M = C,Si, Ge,Sn) : XI. Mercurierung und demercurierung mittels di-t-butylquecksilber, (CH3)3C-Hg-C(CH3)32

Me₃CHgCMe₃ (I) adds to strongly polar CC groups as well as to some CC and NN groups resp., forming t-BuHg containing cis-products. Its reactivity is higher than that of Et₂Hg and equals that of Me₃SiHgSiMe₃ to some extent. In most examples, polar four-center transition states are assumed, but radical reactions occur, too. In the Hg containing adducts investigated, the t-BuHg group can be replaced by the Me₃Sn group easily, by using Me₃SnH. Hg is split off, and i-C₄H₁₀ is evolved quantitatively.     

Reactions of π-allyltricarbonyliron halides and the synthesis of new organoiron compounds

The reactions of [π-C₃H₅Fe(CO)₃X] [where X = Cl (1, Br (2) or I (3)] with different chemical species are described. Thus, 2, and 3 react with Ph₂CNLi in Et₂O to yield [(π-C₃H₅)(CO)₃Fe(NCPh₂)], while the reaction of 1 with PhC(S)N(Me)Li in THF yielded a novel σ-allylironcarbonyl compound. Ethynyl magnesium bromide, HCCMgBr, reacts with 3 in THF to give a π-allyltricarbonyl ethynyliron complex, which undergoes a dipolar cycloaddition reaction with PhCNO in Et₂O, yielding a novel organoiron complex, [(μ-CO)bis{5(σ-allyltricarbonyliron)(3-phenylisoxazole)}]. The reaction of [(π-C₃H₅(CO)₃FeNa] with ClCH₂CH₂NMe₂ is also described. Data on molar conductances, molecular weights, and IR and ¹H NMR spectra, were used to assign structures.     

Thermodynamics of vinyl ethers—XV : Halogen-containing vinyl ethers

Thermodynamics of geometrical and prototropic isomerization reactions on some halogen-containing vinyl ethers of the types ROCH–CHX (X = Cl, Br), ROC(CH₂X)CH₂ (X = F, Cl, Br), and ROC(CHMeCl)CH₂ (R = Me, Et, Et₂CH) have been studied. In ROCH_αCH_βX the cis (or Z) isomer is thermodynamically the more stable isomer, the higher stability of the Z isomer being due to its lower enthalpy. The relative stability of the E and Z forms is, however, reversed if the α H atom is replaced by a Me group. In systems like OCCX the double-bond stabilizing ability of the halogen atom decreases in the order Cl > Br > F, in contrast to the case in haloalkenes, where the corresponding order is F > Cl > Br.     

Überführung eines carben- in einen isocyanid-komplex

Pentacarbonyl(diphenylcarbene)tungsten, (CO)₅WCPh₂ (I), reacts with diethylamino(dimethyl)acetonitrile, Me₂(Et₂N)CCN (II), to give pentacarbonyl(diphenylmethylisocyanide)tungsten, (CO)₅W[CNC(H)Ph₂] (III). In the reaction of I with diethylaminoacetonitrile, H₂(Et₂N)CCN, and dimethylamino(methoxy)acetonitrile, H(MeO)(Me₂N)CCN, respectively, complex III is also formed in small amounts.     

Metal–azo and metal–imine compounds II. : II. Insertion of Ir1 into aromatic and olefinic CH bonds

The reaction of the aromatic azo or imine compounds PhX=NR (X=N or CH; R = alkyl or aryl) and 2-(methylazo)propene, H₂CC(CH₃)N&.zdbnd;NCH₃, with trans-IrCl(N₂)(PPh₃)₂ yields the (ortho) metallated complexes IrHCl(G₆H₄X=NR)(PPh₃)₂ and IrHClCHC(CH₃)-NNCH₃](PPh₃)₂ respectively.The v(N=N) vibration in IrHCl(C₆HZ₄N=NPh)(PPh₃)₂ appears to be drastically lowered with respect to the free ligand vibration. Furthermore, Resonance Raman experiments show that this vibration is strongly coupled to both of the electronic transitions of this compound at longer wavelengths, which therefore must be closely connected with the azo group.¹H and ¹³C NMR spectroscopic data and crystallographic studies of IrHCI(C₆H₄N=NPh)(PPh₃)₂ give strong evidence about the nature of the mechanism of these (ortho) metallation reactions.     

Some diels—alder reactions of η1-bonded cyclopentadienylmetal compounds

Bis(cyclopentadienyl)mercury readily undergoes Diels—Alder reactions with RCCR (R = CO₂Me or CF₃), CF₃CFCFCF₃, CF₃CFCF₂, (CF₃)₂CC(CN)₂, C₂(CN)₄ and Ph$\text{NCONNC}$O to give stable adducts characterised by¹H, ¹⁹F and ¹³C NMR, spectroscopy. Similar reactions of CF₃CCCF₃ and CF₃CFCFCF₃ with the cyclopentadiene derivatives Me₃MC₅H₅ and (Me₃M)₂C₅H₄ (M = Si, Sn) are also described.     

Zur reaktion von metall-koordiniertem kohlenmonoxid mit yliden : VII. Trimethylphosphoranylidenmethyl(trimethylsiloxy)carben-komplexe von chrom,molybdän und wolfram: aufbau einer metallvinyl-einheit durch c(carbanion)c(carben)-π-wechselwirkung und photochemische e/z-isomerisierung

The treatment of the hexacarbonylmetal compounds M(CO)₆ (M = Cr. Mo, W) with two equivalents Me₃PCH₂ yields the phosphonium acylmetalphosphorus ylides Me₄P[(CO)₅MC(O)CHPMe₃] 1a–1c. Their reaction with Me₃SiOSO₂CF₃ leads via O-silylation to formation of the neutral “siloxy(ylidecarbene) complexes” (CO)₅MC(OSiMe₃)CHPMe₃2a–2c, which are protonated by HX (X = Cl, CF₃SO₃) to give the thermolabile carbene complexes [(CO)₅MC(OSiMe₃)H₂CPMe₃]X, 3a, 3b. ¹H, ¹³C NMR and IR data suggest, that delocalization of the ylidic charge to the carbene carbon generates a metal-coordinated vinyl group in the case of 2a–2c. In addition this fact is proved by the X-ray analysis of 2c, for which a C(ylide)C(carbene) bond distance of 133 pm is found. 2a–2c are obtained as pure E-isomers but can be converted to the Z-isomers 2a′–2c′ upon photolysis.     

Trialkylgallium-halogeno-komplexe [R3GaX]− und [(R3Ga)2X]− mit X = F,Cl, Br

The preparation and vibrational spectra of the following complexes are reported: K[R₃GaF] (R = CH₃, C₂H₅), NMe₄[(R₃Ga)₂X] (R = CH₃, C₂H₅; X = F, Cl), NMe₄[Me₃GaBr], NMe₄[(Et₃Ga)₂Br].     

Cumulated double bond systems as ligands : IV. 1H and 13C NMR studies of the intra- and inter-molecular exchange processes of cationic dialkylsulfurdiimine compounds of RhI,IrI and PtII

The preparation and properties are described of trans-[(Ph₃P)₂(CO)M(RNSNR)] [ClO₄] (M  Rh^I, Ir^I; R  Me, Et, i-Pr, t-Bu) and of cis- or trans-[L₂Pt(RNSNR)X] [ClO₄] (X  Cl^?, L  Et₂S, PhMe₂As, PhMe₂P, R  Me, t-Bu; X  CH₃, L  PhMe₂P, R  Me).¹H and ¹³C NMR data show the existence of various isomers in solution which may interconvert via intra- and inter-molecular exchange processes. A general reaction scheme for the intramolecular exchange processes is discussed.     

Alternativ-Liganden. IV. Darstellung von Chelatliganden des Typs Me2XSiMe2CH2X′Me2 (Me = CH3; X,X′ = N,P und/oder As)

Preparation of Chelating Ligands of the Type Me₂XSiMe₂CH₂X′Me₂ (Me = CH₃; X, X′ = N, P and/or As) Chelating Ligands of the general type Me₂XSiMe₂CH₂X′Me₂ (Me = CH₃; X, X′ = N, P As) are obtained from ClSiMe₂CH₂Cl by the following reactions (see “Inhaltsübersicht”). The new compounds have been characterized by analytical and spectroscopic methods (IR, NMR, MS).     

3-Methyl-3-butenenitrile and 3-bromo-2-methyl-1-propene; normal coordinate calculations based on valence force fields

Normal coordinate calculations have been made for the actual conformers of the molecules CH₂C(CH₃)CH₂X, XCN, Br. A valence force field of 37(34) force constants reproduced the 33(30) fundamental frequencies for XCN(Br) to an average deviation of 14(11) cm⁻¹. For 3-bromo-2-methyl-1-propene the calculation suggests a reassignment. According to this, the existing experimental data may be reinterpreted as 3-bromo-2-methyl-1-propene having 2 conformers, instead of 3 as suggested earlier.     

Evaluation des interactions électroniques en série hétérocyclique par la mesure des aires intégrées des bandes infrarouges: Cas de dérivés du benzothiazole substitués en position 2

Infrared νCN vibration bands of some 2-X substituted benzothiazoles (X=H, CH₃, Cl, F, OCH₃, N(C₂H₅)₂, SCH₃ and CN) have been used through their integrated areas, to establish a correlation with substituent characteristic parameters.     

Mass spectrometry of organic compounds in the group V elements—I: Straight chain aliphatic derivatives

Comparative investigations of the mass spectra of eEH₂, Me₂EH, Et₂EH(E = N, P); Me₃E, Et₃E(E = N, P, As, Sb, Bi). (n-Pr)₃E(E = Sb, Bi); (n-Bu)₃E(E = P, As); (n-C₅H₁₁)₃As and (n-C₆H₁₃)₃As as well as Et₂AsBr have been carried out. Deuteroanalogues, metastable transitions and low voltage spectra were used for elucidation of the fragmentation paths. The mass spectra of MeN(CH₂)₂ and CD₃N(CH₂)₂ were studied to analyse the structure of the fragments. The main degradation path of amines, i.e. α-cleavage, was shown to be untypical for P, As, Sb and Bi derivatives.     

Übergangsmetallketen-verbindungen: XXXVIII. Synthese wolframhaltiger fünfringheterocyclen durch addition von trimethylphosphin an phosphino- und arsinoketenkomplexe

The reaction of phosphino- and arsino-ketene complexes of tungsten η⁵-C₅H₅(CO[P(CH₃)₃] XW[η¹-R₂Y(C₆H₄CH₃)CCO] (X = Cl, I; Y = P, As) with trialkylphosphines does not lead to a substitution of the phosphino- and arsinoketene ligands but to a nucleophilic attack of the phosphine at the central ketene carbon and a concomitant substitution of the halogene ligand via the former ketene oxygen, affording the cationic compelex η⁵-C₅H₅(CO)[P(CH₃)₃]W[η²-R₂YC-(C₆H₄CH₃C(PR′₃)O]X and P,O and As,O chelate ligands. The substitution products R₂Y(C₆H₄CH₃)CCO and η⁵-C₅H₅(CO)[P(CH₃)₃]XW(PR′₃) initially expected could only be obtained as a result of a selective rearrangement/elimination reaction as shown in the case of the arsenic substituted complex η⁵-C₅H₅(CO)(PMe₃)IWAs(CH₃)₂C(C₆H₄CH₃)C=O.     

Bromination of silatranyl-, germatranyl-, silyl-, and germyl-phenylacetylenes

Reactions of element-substituted alkynes R₃MCCPh (R₃M = Me₃Si, Et₃Si, Ph₃Si, Et₃Ge, n-Bu₃Sn, N(CH₂CH₂O)₃Si, N(CH₂CH₂O)₃Ge, N(CH₂-CHMeO)₃Ge, and N(CH₂CH₂O)₂(CH₂CHPhO)Ge) with bromine, tetra-n-butylammonium tribromide (TBAT), and N-bromosuccinimide (NBS)/DMSO were investigated. The Z,E-ratio of isomeric dibromoalkenes formed in bromination reaction with Br₂ and TBAT are discussed. The crystal structures of N(CH₂CH₂O)₃SiCCPh and N(CH₂CHMeO)₃GeX (X = C CPh, C(Br)C(Br)Ph, C(Br₂)C(O)Ph), and Ph₃SiC(Br)C(Br)Ph are reported. © 2003 Wiley Periodicals, Inc. 15:43–56, 2004; Published online in Wiley InterScience (www.interscience.wiley.com). DOI 10.1002/.hc10211     

Zur reaktion von metallkoordiniertem kohlenmonoxid mit yliden: XIV. Eisenacyl-phosphor-ylide mit elektronenreicher organometallgruppierung

Treatment of [C₅Me₅(CO)₃Fe]BF₄ (I) with the phosphines Me₃P and Et₃P under thermal or photochemical conditions yields the novel iron salts [C₅Me₅-(CO)₂(R₃P)Fe]BF₄ (R = Me (IIa), R = Et (IIb)) and [C₅Me₅(CO)(Me₃P)₂Fe]BF₄ (IIc). The reaction of I and IIa with two mol of the ylide Me₃PCH₂ leads to the formation of the ironacyl-ylides C₅Me₅(CO)(L)FeC(O)CHPMe₃ (L = CO (IVa), Me₃P (IVb)). IVa selectively reacts at the “ylidic” carbon with the electrophilic reagents MeI, MeOSO₂F, Me₃SiOSO₂CF₃ to give the ironacyl-phosphonium salts [C₅Me₅(CO)₂FeC(O)CH(R)PMe₃] X (VaVc), while IVb is partially converted to [C₅Me₅(CO)₂FeC(O)CH₂PMe₃]BF₄ (IIIa) is obtained together with [C₅Me₅-(CO)₂Fe]₂ from I and IVa.