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.     

Die Kristall- und Molekülstrukturen von In(CH3COO)3 · 2,2′-Dipyridin und In(CH3COO)3 · 1,10-Phenanthrolin – Verbindungen mit Indium der Koordinationszahl 8

Crystal and Molecular Structures of In(CH₃COO)₃ · 2,2′-Dipyridine and In (CH₃COO)₃ · 1,10-Phenanthroline – Compounds of Indium with Coordination Number 8 In(CH₃COO)₃ · 2,2′-dipyridine and In(CH₃COO)₃ · 1,10-phenanthrline crystallize in the monoclinic space group P2₁/c with a = 844.7(3), b = 1 408.8(5), c = 1 466.6(5) pm, β = 84.9(1)°, Z = 4 (dipyridine complex) and a = 811.9(3), b = 1 555.3(5), c = 1 447.3(5) pm, β = 90.6 (1)°, Z = 4 (phenanthroline complex). The structures were determined by the heavy atom method from 2202 and 2617 independent reflections and have been refined by full matrix least-squares methods to R = 3.49 and 4.35%, respectively. In both complexes the acetate ligands and the N-donor ligand are bidentate, In attaining the coordination number 8. The donor atoms are arranged in the form of a distorted dodecahedron. Some distances and angles: see ?Inhaltsübersicht”?.     

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.     

Verbindungen des Germainums und Zinns. 17. Alkylarylstannylen-Komplexe des Chroms und Molybdäns ohne Donorstabilisierung

Compounds of Germanium and Tin. 17 [1]. Alkylarylstannylene Complexes of Chromium and Molybdenum without Donor Stabilization Reaction of the complexes [(OC)₅M(THF)], M = Cr, Mo, with the alkylarylstannylene RR′Sn: R = 2,4,6-tBu₃C₆H₂, R′ = CH₂C(CH₃)₂-3,5-tBu₂C₆H₂, provides the donor-free stannylene complexes [(OC)₅Cr?SnRR′] ( 6 ) and [(OC)₅Mo?SnRR′] ( 8 ), respectively. The X-ray structure analyses of the isotypic compounds 6 and 8 reveal the three coordinate tin atoms in strictly planar environments and acute CSnC angles of 91.2° ( 6 ) and 91.3° ( 8 ).     

The aerobic methylation of arsenic by microorganisms in the presence of l-methionine-methyl-d3

The microorganisms Scopulariopsis brevicaulis, Candida humicola, and Gliocladium roseum growing aerobically, methylate a range of arsenic compounds to produce R′R″As(CH₃) (R′  R″  CH₃; R′  n-C₄H₉, R″  CH₃). When l-methionine-methyl-d₃ is added to the cultures the CD₃ label is incorporated, intact, in the evolved arsine to a considerable extent, indicating that S-adenosylmethionine or some related sulphonium compound is involved in the biological process.     

Organische Phosphorverbindungen XXXI. Ein einfaches Verfahren zur Herstellung von Alkylen- bzw. Arylen- bzw. diphosphiniten und von Bis-(dialkyl- und diaryl-phosphinyl)-alkanen

The reactions of dialkylamino-dialkyl- or diaryl-phosphines, R₂PNR′₂ (R = C₆H₅ C₄H₉, C₂H₅; R′ = CH₃, C₂H₅) with unsaturated alcohols, functional alcohols, α, ω-alkane-diols and α, ω-alkane-dithiols have been studied. The preparation of a large number of alkylene (or arylene) bis-phosphinites and of bis-phosphinyl-alkanes is reported and their physical properties listed.     

Untersuchungen an Alkylmetallalkoxiden der Elemente Aluminium,Gallium und Indium. I. Die Schwingungsspektren von Dimethylaluminiummethoxid und Methylmethoxialuminiumchlorid

Studies on Alkyl Metal Alkoxides of Aluminium, Gallium, and Indium. I. The Vibrational Spectra of Dimethylaluminiummethoxide and Methylmethoxyaluminiumchloride. The vibrational spectra (IR and RAMAN ) of dimethylaluminium methoxide and deuteromethoxide have been measured and assigned. These trimeric alkoxides consist of puckered six-membered AL₃O₃ ring skeletons probably of C₃ or C₂ symmetry. The structure of methylmethoxyaluminiumchloride could not be determined definitely from the spectroscopic data.     

Alkyl- und Arylkomplexe des Iridiums und Rhodiums. XIX. Reaktion von Carbonsäuren mit ausgewählten Organoverbindungen von Ir(I) und Rh(I): Bildung von Arylhydrido-, Carboxylatohydrido- und Carboxylato-Derivaten

Alkyl and Aryl Complexes of Iridium and Rhodium. XIX. Reaction of Carboxylic Acids with Selected Organo Compounds of Ir(I) and Rh(I): Formation of Arylhydrido, Carboxylatohydrido, and Carboxylato Derivatives cis-Arylhydridoiridium(III) complexes IrH(Ar)(O₂CR)(CO)(PPh₃)₂ (R = Me: Ar = C₆H₅, 4-MeC₆H₄; R = Et: Ar = 4-MeC₆H₄, 2,4-Me₂C₆H₃) could be prepared by oxidative addition of carboxylic acids to aryliridium(I) compounds Ir(Ar)(CO)(PPh₃)₂. Reaction of aliphatic carboxylic acids with alkyliridium(I) derivatives Ir(Alk)(CO)(PPh₃)₂ and Ir(Alk)[PhP(CH₂CH₂CH₂PPh₂)₂] (Alk = CH₂CMe₃, CH₂SiMe₃) lead to dicarboxylatoiridium(III) hydrides IrH(O₂CR)₂(CO)(PPh₃)₂ (R = Me, Et, i-Pr) and IrH(O₂CR)₂[PhP(CH₂CH₂CH₂PPh₂)₂] (R = Me, Et). Ir(4-MeC₆H₄CO₂)(CO)(PPh₃)₂ was obtained from Ir(CH₂SiMe₃)(CO)(PPh₃)₂ and 4-MeC₆H₄CO₂H. Interaction of organorhodium complexes Rh(R′)(CO)(PPh₃)₂ (R′ = CH₂SiMe₃, 4-MeC₆H₄) and Rh(R′)[PhP(CH₂CH₂CH₂PPh₂)₂] (R′ = CH₂CMe₃, 4-MeC₆H₄) with aliphatic and aromatic carboxylic acids yielded carboxylatorhodium(I) compounds Rh(O₂CR)(CO)(PPh₃)₂ (R = Me, t-Bu, 4-MeC₆H₄) and Rh(O₂CR)[PhP(CH₂CH₂CH₂PPh₂)₂] (R = Me, 4-MeC₆H₄).     

O-Halogensilyl-N,N-bis(trimethylsilyl)hydroxylamine – Synthese,Kristallstruktur und Reaktionen

O-Halogenosilyl-N,N-bis(trimethylsilyl)hydroxylamines – Synthesis, Crystal Structure, and Reactions The substitution of halogenosilanes on lithiated N,O-bis(trimethylsilyl)-hydroxylamine in the molar ratio of 1 : 1 occurs on the oxygen atom. The O-halogenosilyl-N,N-bis(trimethylsilyl)hydroxylamines were prepared: RSiF₂ON · (SiMe₃)₂ (R = CMe₃ 1 , CHMe₂ 2 , CH₂C₆H₅ 3 , C₆H₂(CMe₃)₃ 4 ), RR′SiFON(SiMe₃)₂ (R = CMe₃, R′ = C₆H₅ 5 ; R = Me, R′ = C₆H₅ 6 ; R = C₆H₂Me₃, R′ = C₆H₂Me₃ 7 ; R = CH₂C₆H₅, R′ = CH₂C₆H₅ 8 ; R = CHMe₂, R′ = CHMe₂ 9 ; R = CMe₃, R′ = CMe₃ 10 ), RSiCl₂ON(SiMe₃)₂ (R = CMe₃ 11 ; R = Cl 12 ). The reaction of fluorosilanes with lithiated N,O-bis(trimethylsilyl)hydroxylamine in the molar ratio of 1 : 2 leads to the formation of O,O′-fluorosilyl-bis[N,N-bis(trimethylsilyl)hydroxylamines]: RSiF[ON(SiMe₃)₂]₂ (R = CMe₃ 13 ; R = C₆H₅ 14 ). 13 could be prepared in the reaction of 1 with LiON(SiMe₃)₂. Lithiated dimethylketonoxime reacts with 1 to Me₂C=NOSiRF–ON(SiMe₃)₂ [R = CMe₃ ( 15 )]. The first crystal structure of a tris(silyl)hydroxylamine ( 4 ) is shown. The angle at the nitrogen prove a pyramidal geometry.     

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 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.     

Organometallic and organobimetallic complexes of platinum(II) containing 2,2′-bipyrimidyl: syntheses and spectroscopic characteristics

Preparations are described of several monometallic complexes (bipym)PtR₂ [bipym = 2,2′-bipyrimidyl; R = Me, CF₃, Ph, 1-adamantylmethyl (adme); R₂ = (CH₂)₄] and bimetallic analogues R₂Pt(μ-bipym)PtR′₂ [R = R′ = CH₃, C₆H₅, adme; R = CH₃, R′ = Ph, adme, CF₃]. IR, ¹H NMR and UV/visible spectroscopic characteristics of the two modes of bipyrimidyl coordination are discussed.     

Thermally stable rigid π-allylnickel compounds, (π-CHRCR′CR2)Ni(PPhMe2)C6Cl5

The reaction of C₆Cl₅Ni(PPhMe₂)₂Cl with CHRCR′CH₂MgX (X = Br or Cl) yields π-allylnickel compounds, (π-CHRCR′CH₂)Ni(PPhMe₂)C₆Cl₅ (Ia, R = R′ = H; Ib, R = H, R′ = CH₃; Ic, R = CH₃, R′ = H), which are stable in the solid state below ca. 150°C and are fairly stable in solution in the absence of oxygen. The π-allyl group was found by PMR spectroscopy to be rigid even in the presence of an excess of PPhMe₂, P(OEt)₃ or P(OMe)₃.     

Pentafluorsulfanylamine und Sulfanylammonium-Salze

Pentafluorosulfanylamines and Sulfanylammonium Salts . From the addition of HF to sulfurtetrafluorideimides N-alkylpentafluorosulfanylamines RNHSF₅(2a, 2b: R=CH₃, C₂H₅) are obtained in quantitative yield. N, N-dialkylpentafluorosuIfanylamines Et₂NSF₅(5a) and pip-SF₅ (5b) are isolated from the reaction of the appropriate sulfurdifluoronitridearnides NSF₂NR₂ and HF/SF₄. Protonation of the amines with the superacidic system HF/AsF₅ gives stable pentafluorosulfanyl-ammonium salts SF₅NHRR′_. AsF₆ (12: R = R′ = CH₃; 14: R=R′=H; 10: R=CH₃, R′ = H). Under the same conditions the adduct AsF₅· NSF₂CF(CF₃)₂ (15) forms a cation with hexacoordinated sulfur (trans-H₃NSF₄CF(CF₃)₂^?AsF₆⁶: 16), while with Asp₅ · NSF₂NMe₂ (17) the reaction stops at tetracoordination (HNSF₂NMe₂⁺AsF₆ : 18).     

Über organogermaniumtrisulfinsäureester und versuche zur darstellung von tetrasulfinsäureestern des germaniums

The trisulfinic esters of germanium RGe(O₂SR′)₃ (R = R′ = CH₃; R = C₆H₅, R′ = CH₃, C₂H₅), which are sensitive to hydrolysis and temperature, are obtained by reaction of the corresponding trichlorides RGeCl₃ with anhydrous silver sulfinates. Aromatic trisulfinic esters as well as tetrasulfinic esters of germanium could not be obtained because of steric reasons. The esters, in which the RSO₂^?-residues are linked to germanium via oxygen, are investigated on the basis of their ¹H NMR, mass, IR and Raman spectra.     

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.     

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.     

Synthesis and characterization of some novel triphenylarsenic(V) derivatives of monofunctional bidentate 2,2‐disubstituted benzothiazoline ligands

A series of triphenylarsenic(V) derivatives Ph₃As(OPrⁱ)[SC₆H₄N:C(R)CH₂C(O)R′] have been synthesized by the reactions of triphenylarsenic(V)‐ isoproproxide, Ph₃As(OPrⁱ)₂ with the corresponding 2,2‐disubstituted benzothiazolines of the type (where R = CH₃, R′ = CH₃( 1 ); R = CH₃, R′ = C₆H₅( 2 ); R = CH₃, R′ = 4‐CH₃C₆H₄( 3 ); R = CH₃, R′ = 4‐ClC₆H₄( 4 ); and R = CF₃, R′ = C₆H₅( 5 )) in equimolar ratio in refluxing benzene solution. Molecular weight measurements of these complexes show their monomeric nature in solution. Characterization of these compounds using elemental analyses, molecular weight measurements, and spectral studies (IR as well as NMR (¹H and ¹³C)) shows the monofunctional bidentate nature of the ligands and a hexacoordination around the central arsenic atom in these organoarsenic(V) derivatives. © 2007 Wiley Periodicals, Inc. Heteroatom Chem 18:76–80, 2007; Published online in Wiley InterScience ( www.interscience.wiley.com ). DOI 10.1002/hc.20233     

Derivate des borabenzols: XVI. (Borinato)(cyclobutadien)cobalt-komplexe mit tetramethyl- und tetraphenylcyclobutadien-liganden. Synthese,elektrophile aromatische substitution und ringgliedsubstitution am borinato-liganden

The preparation of (borinato)(cyclobutadiene)cobalt complexes from the reactions of Co(C₅H₅BR)(1,5-C₈H₁₂) with acetylenes C₂R′₂ and of [C₄(CH₃)₄]Co(CO)₂I with Tl(C₅H₅BR) (R,R′ = CH₃, C₆H₅) is described.In electrophilic substitution reactions Co(C₅H₅BCH₃)[C₄(CH₃)₄] (IVa) is more reactive than ferrocene. CF₃CO₂D effects H/D-exchange in the α-position of the borabenzene ring within a few minutes at ambient temperature and in the γ-position within less than four hours Friedel-Crafts acetylation with CH₃COCl/AsCl₃ in CH₂Cl₂ affords the 2-acetyl and the 2,6-diacetyl derivative of IVa. With the more active catalyst AlCl₃, ring-member substitution is effected to give cations [Co(arene)C₄(CH₃)₄]⁺ (arene = C₆H₅CH₃, 2-CH₃C₆H₄COCH₃). Vilsmeier formylation gives the 2-formyl derivative of IVa. The acyl derivatives Co(2-R¹CO-6-R²C₅H₃BCH₃)[C₄(CH₃)₄] (R¹ = CH₃, R² = H, CH₃CO and R¹ = R² = H) transform to the corresponding cations [Co(ortho-R¹R²C₆H₄)C₄(CH₃)₄]⁺ in superacidic media. The mechanistic relationship between acylation and ring-member substitution is discussed in detail.     

Über Cyanatverbindungen und deren reaktives Verhalten. XXI. Reaktionsverhalten von Niob(V)- und Tantal(V)-thiocyanat gegenüber N-Donatoren

Cyanate Compounds and their Reactivity. XXI. Reactivity of Niobium(V) and Tantalum(V) Thiocyanates to N-Donators M₂(NCS)₁₀ reacts with ammonia or primary and secondary aliphatic amines to complexes of the types [M(NCS)(NH₂)₂NH]_x, [M(NCS)₃(NHR)₂ H₂NR], or [M(NCS)₃(NR′₂)₂ HNR′₂], with N-heterocyclic amines in a first step to [M(NCS)₅L]-complexes and in a further step through a redox mechanism to [M(NCS)₄L₂] complexes. [M(NCS)₅(CH₃CN)] mCH₃CN reacts with ammonia, or primary amines in acetonitrile over acetamidine and amidinolytic cleavage of M-NCS bonds to complexes of the type [M(NCS)_a(NC(NHR″)CH₃)_b(CH₃C(NH)NHR″)]_x. The prepared compounds are characterized by analytical data, derivatographic measurements, and IR or visible absorption spectra (M = Nb, Ta; x = 2; R = n-C₄H₉; R′ = C₂H₅; L = pyridine or 4-methyl-pyridine; m = 0, 1, 2; a = 1 or 4; b = 4 or 1; R″ = H, n-C₄H₉).