Metallorganische Lewis-Säuren. XLII. Carbonyl- und Nitrosyl-Komplexe von Mangan und Rhenium mit schwach koordinierten Anionen (Ph3P)2(ON)2MnX, (Ph3P)n(OC)5–nMX (M = Mn,Re; n = 1, 2; X = FBF3, OSO2CF3, OSO2F,OCORf)

Organometallic Lewis Acids. XLII. Carbonyl- and Nitrosyl Complexes of Manganese and Rhenium of Weakly Coordinated Anions (Ph₃P)₂(ON)₂MnX, (Ph₃P)_n(OC)_5–nMX (M = Mn, Re; n = 1, 2; X = FBF₃, OSO₂CF₃, OSO₂F, OCOR_f) The complexes (Ph₃P)₂(ON)₂MnX (X = FBF₃, OSO₂CF₃, OSO₂F, OCOCF₃, OCOC₃F₇) and (Ph₃P)_n(OC)_5–nMX (M = Mn, Re; n = 1, 2; X = FBF₃, OSO₂CF₃) have been obtained by reaction of (Ph₃P)₂(ON)₂MnH and (Ph₃P)_n(OC)_5–nMeMe with the corresponding acids HX or from (Ph₃P)_n(OC)_5–nReBr (n = 1, 2) with silver salts AgX, respectively. The compounds have been characterized by their IR and partially by ¹⁹F-NMR data. An efficient method for the preparation of the hydride (Ph₃P)₂(ON)₂MnH is reported.     

Vinylierung und 91Zr-NMR-Spektren von Substituierten Zirconocendichloriden

Vinylation and ⁹¹Zr N.M.R. Spectra of substituted Zirconocene Dichlorides Substituted zirconocene dichlorides react with vinyl lithium with formation of zirconacyclopent-2-enes, Cp₂ZrCH = CHCH₂CH₂, or zirconocene butadiene complexes, Cp₂Zr(C₄H₆). The compounds obtained were characterized by their ¹H and ¹³C n.m.r. spectra. The ⁹¹Zr n.m.r. chemical shifts of substituted zirconocene dichlorides correlate with the bond angles Cp′? Zr? Cp′ and Cl? Zr? Cl respectively. They can be used to estimate the reaction behaviour of zirconocene dichlorides.     

Beiträge zur Chemie der Alkylverbindungen von Übergangsmetallen. 62. Darstellung und NMR-spektroskopische Untersuchung von Komplexen des Tetramethyltitans

Contributions to the Chemistry of Transition Metal Alkyl Compounds. 62. Preparation and NMR-spectroscopic Characterization of Tetramethyltitanium Complexes Complexes of tetramethyltitanium with THF and oxygen, nitrogen and phosphorous containing chelating ligands were synthesized and characterized by low temperature n.m.r. spectroscopy. The obtained complexes show a dynamic behaviour in solutions. The results of semiempirical MO calculations favour octahedral and not a trigonal prismatic configuration of the complexes.     

Über die Darstellung der N-Chlor-N-Methylammoniumsalze (CH3)nNCl4–n+MF6− (n = 1–3; M = As,Sb) und (CH3)2NCIX+MF6− (X = F,Br)

About the Preparation of N-Chloro-N-Methylammonium Salts (CH₃)_nNCl_4–n⁺MF₆^? (n = 1–3; M = As, Sb) and (CH₃)₂NClX⁺MF₆^? (X = F, Br) Simple one-step methods for the preparation of the methylated chloroammonium salts (CH₃)_nNCl_4–n⁺MF₆^? (n = 1–3; M = As, Sb) and for (CH₃)₂NClX⁺MF₆^? (X = F, Br) are reported. Their vibrational and NMR-spectroscopical data are discussed in comparison.     

Darstellung und Charakterisierung von [N-(2-Mercaptoacetyl)-N′ -4-(penten-3on-2)ethylen-1,2-diaminato]oxorhenium(V), ReO(MRP 40)

Synthesis and Characterization of [N-(2-Mercaptoacetyl)-N′ -4-(penten-3on-2)ethylen-1,2-diaminato]oxorhenium(V), ReO(MRP 40) The title complex is obtained in good yields from the reaction of the triphenylmethyl-protected ligand with (Bu₄N)ReOBr₄ or ReOCl₃(Ph₃P)₂. The structure of the compound as neutral oxorhenium(V) complex is confirmed by analytical, ¹H-, ¹³C-NMR, IR, UV/Vis as well as mass spectrometric studies.     

Darstellung,Eigenschaften und elektronische Raman-Spektren von Bis(chloro)phthalocyaninatoferrat(III), -ruthenat(III) und -osmat(III)

Preparation, Properties and Electronic Raman Spectra of Bis(chloro)-phthalocyaninatoferrate(III), -ruthenate(III) and -osmate(III) Bis(chloro)phthalocyaninatometalates of Fe^III, Ru^III and Os^III [MCl₂Pc(2-)]^?, with an electronic low spin ground state are formed by the reaction of [FeClPc(2-)] resp. H[MX₂Pc(2?)] (M = Ru, Os; X = Cl, I) with excess chloride in weakly coordinating solvents (DMF, THF) and are isolated as (n-Bu₄N) salts. The asym. M? Cl stretch (ν_as(MCl)) is observed in the f.i.r. at 288 cm^?1 (Fe), 295 cm^?1 (Ru), 298 cm^?1 (Os), ν_as(MN) at 330 cm^?1 (Fe), 327 cm^?1 (Ru), and 317 cm^?1 (Os); only ν_s(OsCl) at 311 cm^?1 is resonance Raman (r.r.) enhanced with blue excitation. The m.i.r. and FT-Raman spectra are typical for hexacoordinated phthalocyanines of tervalent metal ions. The UV-vis spectra show besides the characteristic π-π* transitions (B, Q, N, L band) of the Pc ligand a number of extra bands at 12–15 kK and 18–24 kK due to trip-doublet and (Pc→M)CT transitions. The effect of metal substitution is discussed. The r.r. spectra obtained by excitation between the B and Q band (λ₀ = 476.5 nm) are dominated by the intraconfigurational transition Γ₇ Γ ₈ arrising from the spin-orbit splitting of the electronic ground state for Fe^III at 536 cm^?1, for Ru^III at 961 cm^?1 and Os^III at 3 028 cm^?1. Thus the spin-orbit coupling constant increases very greatly down the iron group: Fe^III (357 cm^?1)< Ru^III (641 cm^?1)< Os^III (2 019 cm^?1). The Γ₇ Γ ₈-transition is followed by a very pronounced vibrational finestructure being composed in the r.r. spectra by the coupling with ν_s(MCl), δ(MClN) and the most intense fundamental vibrations of the Pc ligand. In absorption only vibronically induced transitions are observed for the Ru and Os complex at 1 700-2800 rsp. 3100-5800 em^?1 instead of the 0-0 phonon transitions. The most intense lines are attributed to combinations of the intense odd vibrational mo-des at ≈ 740 and 1120 cm^?1 with ν₅(MCI), δ(MClN).     

Darstellung und spektroskopische Eigenschaften von Nitridophthalocyaninatorhenium(V)

Preparation and Spectroscopical Properties of Nitridophthalocyaninatorhenium(V) Nitridophthalocyaninatorhenium(V) ([ReNPc^2?]) is prepared by the reaction of dirheniumheptoxide with ammoniumiodide in molten 1,2-dicyano-benzene. The diamagnetic complex is chemically und thermically extremely stable. In the Uv-vis spectra the typical π-π*-transitions of the Pc^2? ligand are observed. Extra bands in the solid state spectrum are due to strong excitonic coupling of ca. 2.8 kK. In the resonance Raman spectra the intensity of the Re≡N stretching vibration (v(Re≡N)) at 969 cm^?1 is selectively enhanced by laser excitations above 19.0 kK. v(Re≡N) is a dominant m.i.r. absorption at 976 cm^?1.     

Komplexchemie P-reicher Phosphane und Silylphosphane. IV. Bildung und Struktur der Chromcarbonylkomplexe des Tris(di-tert-butylphospha)heptaphosphanortricyclans, (t-Bu2P)3P7

Transition Metal Complexes of P-rich Phosphanes and Silylphosphanes. IV. Formation and Structure of the Chromium Carbonyl Complexes of Tris(di-tert-butylphospha)heptaphosphanortricyclane (t-Bu₂P)₃P₇ The reaction of (t-Bu₂P)₃P₇ 1 with Cr(CO)₅ · THF in a molar ratio of 1:1 yields yellow crystals of (t-Bu₂P)₃P₇[Cr(CO)₅] 2 having the Cr(CO)₅ group coordinated to a P^b atom (basal) of the three membered ring. With a molar ratio of 1:2 compounds 2 , (t-Bu₂P)₃P₇[Cr(CO)₅]₂ 3 , (t-Bu₂P)₃P₇[Cr(CO)₅][Cr(CO)₄] 4 and (t-Bu₂P)₃P₇[Cr(CO)₄]₂ 5 were obtained. In 3 (yellow crystals) one Cr(CO)₅ group is linked to a P^b atom, the other one to an exocyclic P^exo atom. On irradiation 3 loosing one CO group generates 4 (orange red crystals) with an unchanged Cr(CO)₅ group linked to the Pb atom and a five membered chelate-like ring containing an apical Pa atom, two equatorial P^a atoms, one P^exo atom and the Cr atom of the carbonyl group. Compound 5 (orange red crystals) contains two such five membered rings. (t-Bu₂P)₃P₇[Cr(CO)₄]₃ 6 (red needles) is formed with Cr(CO)₅ · THF in a molar ratio of 1 : 1. However, even with higher amounts of Cr(CO)₅ · THF and after extended reaction times, only 6 is formed; no further Cr carbonyl group could be attached to the P skeleton. With Cr(CO)₅ · NBD in a molar ratio of 1 : 1, (t-Bu₂P)₃P₇[Cr(CO)₄] 7 is produced from 1, and 5 with a molar ratio of 2 : 1. As in 4, the Cr(CO)₄ group in 7 (orange crystals) participates in a five membered chelate-like ring. It was not possible to generate 6 from 5 with an excess of Cr(CO)₄ · NBD and with extended reaction times. The molecular structures of the compounds were identified by investigating the ³¹P[¹H] NMR spec-tra and considering especially the coordination shift, and by crystal structure determinations of 2 and 4. Compound 2 crystallizes in the space group PI (no.2) with a = 1566.2(4) pm, b = 2304.1(5) pm, c = 1563.3(4) pm,α = 95.57(3)°, β = 108.79(3)°, γ = 109.82(4)° and Z = 4 formula units in the elementary cell. Compound 4 crystallizes in the space group P 2₁ /n (no. 14) with a = 1416.6(5) pm, b = 2573.6(5) pm, c = 1352.9(4) pm,β = 99.17(5)° and Z = 4 formula units in the elementary cell.     

Tris(trimethylsilyl)methanselenenylhalogenide und -chalkogenide

Tris(trimethylsilyl)methaneselenenyl Halides and Chalcogenides . Ditrisyldiselenide ( 1 ) (trisyl = TSi = (Me₃Si)₃C) reacts with SOCl₂, Br₂ and I₂ to provide trisylselenenyl halides TSiSeX ( 2 : X = Cl; 3 : X = Br, 4 : X = I). Insertion of S and Se into the Se? Se bond of 1 to yield (TSiSe)₂S_n ( 5 : n = 1; 6 : n = 2) and (TSiSe)₂Se_n ( 7 : n = 1; 8 : n = 2) was catalysed by iodine. 5 was isolated in pure state and examined by X-ray diffraction. Triselenide 7 can be cleaved by I₂ in CS₂ to give 4 and Se₂I₂ ( 9 ). From 2 with Me₃SiCN and Me₃SiNCS, the new selenenyl pseudohalides TSiSeCN ( 10 ) and TSiSeSCN ( 11 ) were prepared. The compounds were characterised by ¹H, ¹³C- and ⁷⁷Se n.m.r. spectra.     

Darstellung und spektroskopische Charakterisierung von Di(acido)phthalocyaninatorhodaten(III)

Preparation and Spectroscopical Characterization of Di(acido)phthalocyaninatorhodates(III) Triethylendiaminorhodiumiodide reacts quickly and completely with boiling phthalodinitrile precipitating ?rhodiumphthalocyanine”?, which is purified and dissolved in alkaline media as di(hydroxo)phthalocyaninatorhodate(III). Acidification in the presence of halides or pseudohalides yields less soluble acidophthalocyaninatorhodium reacting with tetra-n-butyl-ammonium(pseudo)halide to give (blue)green tetra-n-butyl-ammoniumdi(acido)phthalocyaninatorhodate(III), (ⁿBu₄N)[Rh(X)₂Pc^2?] (X = Cl, Br, I, N₃, CN, NCO, SCN, SeCN). The asym. Rh? X-stretching vibration (v_as(RhX)) is observed in the f.i.r. at 290 (X = Cl), 233 (Br), 205 (I), 366 (N₃), 347 (CN), 351 (NCO), 257 (SCN) and 214 cm^?1 (SeCN). v_s(RhI) is the only sym. Rh? X-stretching vibration excited at 131 cm^?1 in the Raman spectrum. The m.i.r. and resonance Raman spectra are typical for hexacoordinated phthalocyaninatometalates(III). The influence of the axial ligands is very small. The frequency of the stretching vibrations of the pseudohalo-ligands are as expected (in the case of the ambident ligands the bonding atom is named first): v_as(NN) at 2006 and v_s(NN) at 1270 cm^?1 (N₃); v_as(CN) at 2126 (CN), 2153 (NCO), 2110 (SCN) and 2116 cm^?1 (SeCN). The characteristic π–π*-transitions of the Pc^2?-ligand dominate the UV-vis spectra. The splitting of the Q and N region is discussed and the weak absorbance at ca. 22 kK is assigned to a n–π*-transition.     

Darstellung der Iminiumsalze CF3?NXCF2+MF6− (X = CH3, F und M = As,Sb) und CF3?NCl = CF2+ AsF6−

Preparation of the Iminium Salts CF₃? NX?CF₂⁺MF₆^? (X = CH₃, F and M = As, Sb) and CF₃? NCl?CF₂⁺ AsF₆^? The preparation of the iminiumsalts CF₃? NX?CF₂⁺ MF₆^? (X = CH₃, F and M = As, Sb) and CF₃? NCl?CF₂⁺ AsF₆^? is reported. The salts were characterized by NMR and infrared spectroscopy. CF₃? NCH₃?CF₂⁺MF₆^? decompose into MF₅ and (CF₃)₂NCH₃.     

Neutrale Bora-Silatropie an B-Halogen-substituierten Boryl-bis(silyl)hydroxylaminen

Neutral Rearrangement between Boryl and Silyl Groups in B-Halogenosubstituted Boryl-bis(silyl)hydroxylamines Dihalogenboranes, RBX₂, react with lithiated N,O-Bis(trimethylsilyl)hydroxylamine to give B-halogeno-borylhydroxylamines RB(X)ON(SiMe₃)₂: X = F, R = Trip (Trip = 2,4,6-triisopropylphenyl) ( I a ), N(SiMe₃)₂ ( I b ), N(CHMe₂)₂ ( I c ), N(SiMe₃)Dip (Dip = 2,6-diisopropylphenyl) ( I d ) and X = Cl, R = N(SiMe₃)₂ ( I e ). Depending upon the substituents on the boron atom a dyotropic rearrangement can be effected which transforms the compounds I a , I b und I e into the isomeric borylhydroxylamines RB(X)N(SiMe₃)OSiMe₃ II a , II b and II e . The compounds are characterized by their m. s. and n. m. r. (¹H, ¹¹B, ¹³C, ¹⁹F, ²⁹Si) spectra and by elemental analyses.     

High-spin Mangan(II)-Phthalocyanine: Darstellung und spektroskopische Eigenschaften von Acidophthalocyaninatomanganat(II)

High Spin Manganese(II) Phthalocyanines: Preparation and Spectroscopical Properties of Acidophthalocyaninatomanganate(II) Acidophthalocyaninatomanaganese(III) is reduced by boranate, thioacetate or hydrogensulfide to yield acidophthalo-cyaninatomanganate(II) ([Mn(X)Pc^2?]^?; X = Cl, Br, NCO, NCS) being isolated as tetra(n-butyl)ammonium salt. In the cyclovoltammogram of [Mn(NCO)Pc^2?]^? the halv-wave potential for the redoxcouple Mn^II/Mn^III is at ?0.13 V, that of the first ring reduction at ?0.99 V. The magnetic moments are indicative of high-spin ⁶A₁ ground states: μ_Mn = 5.84 (NCO), 5.78(Cl), 5.65 (Br), 5.68 μ_B (NCS). A Curie-like temperature dependence of μ_Mn is observed in the region 300–30 K. Below 30 K an increase in μ_Mn occurs due to weak intermolecular ferromagnetic coupling. The ESR spectra confirm the S = 5/2 ground state with a strong g = 6 resonance observed (A_Mn = 80 G) as expected for an axially distorted ligand-field. Besides the typical π-π* transitions of the Pc^2?-ligand several weak bands are observed in the Uv-vis-n.i.r. spectra at ca. 7.5, 9.1, 14.0 and 19.0 kK that are assigned to trip-multiplet transitions. In resonance with the band at 19.0 kK the Mn? X stretching vibration (v(MnX)) is resonance Raman enhanced: X = NCO: 319, Cl: 286, SCN: 238, Br: 202 cm^?1. These vibrational frequencies are confirmed by the f.i.r. spectra. In the case of the thiocyanato-complex probably both forms of bonding of the ambident NCS-ligand are present (v(Mn? NCS): 274 cm^?1). The frequencies of the vibrations of the inner (CN)₈ ring are reduced by up to 20 cm^?1 as compared with those of low spin Mn^II phthalocyanines.     

Borchelate und Bormetallchelate, 4. Mitt.

The i.r., u. v.,¹H n.m.r.,¹³C n.m.r., and¹¹B n.m.r. spectra of several substituted diphenylboron chelates derived from salicylaldehyde azomethines were compared with respect to the influence of the amine substituentR. O–B–N-6-ring constitution of the chelates29–32 [R=OH, NH₂, NHC₆H₅, N(CH₃)₂] can be deduced from the spectra.

Als 3. Mitt. gilt:F. Umland undE. Hohaus mit Beiträgen vonW. Riepe, K. Brodte, C. Schleyerbach undD. Szonn. Untersuchungen über borhaltige Ringsysteme vom Chelattyp. Forschungsbericht des Landes Nordrhein-Westfalen Nr. 2538. Opladen: Westdeutscher Verlag. 1976.     

Subgroup 4 (Ti,Zr, Hf) derivatives of Cobalt Carbonyls

Bimetallic and trimetallic compounds containing unsupported bonds of subgroup 4 metals (M = Ti, Zr, Hf) and Co were prepared by hydride elimination (A) from RM derivatives (R¹ = PhCH₂; RN; R² = Me, Et)) and by salt elimination (B) from RMX (X = Cl, Br; R.¹ = PhCH₂, RN and R³O; R³= i-Pr, n-Bu)) by reaction with HCo(CO)₄ and Na[Co(CO)₄], respectively. Compounds RMCo(CO)₄ with R¹ = PhCH₂, RM[Co(CO)₄]₂ R.¹ = PhCH₂, were prepared both by methods A and B, while (R³O)₄-n Ti[Co(Co)₄]n (n = 1, 2) compounds were obtained by reaction B. Several tertiary phosphine and phosphite derivatives of the former two types were obtained by substitution of a carbonyl group by PR ligand or by A type reaction of HCo(CO)³(PR with RM compounds.     

Darstellung und Eigenschaften von N,N-Dialkyl-allylaminoboran-Addukten und N,N-Dimethyl-aminopropylboran

Synthesis and Properties of N,N-Dialkyl-allylaminoboranes and N,N-Dimethylaminopropylborane Complexes of the type H₃B ← NR₂(CH₂CH?CH₂) (R?CH₃ I , C₂H₅ II ) are formed by reaction of Li[BH₄] with dialkylallylammonium salts. By addition of AlCl₃ I can be transformed into the chelate-stabilized N,N-dimethyl-aminopropylborane III . The i.r.-, ¹H, ¹³C-n.m.r. and mass-spectra of I – III are reported and discussed.     

2,6-Bis(methylencyclopentadienyl)-pyridin-zirconocen- und -hafnocendichlorid; Bildung und Kristallstruktur von [C5H3N-2,6-(CH2?C5H4)2Zr(Cl)(OH2)]2[ZrCl6]

2,6-Bis(methylenecyclopentadienyl)-pyridine-zirconocene and -hafnocene Dichloride; Formation and Crystal Structure of [C₅H₃N-2,6-(CH₂? C₅H₄)₂Zr(Cl)(OH₂)[ZrCl₆]] Pyridine bridged metallocene dichlorides of type C₅H₃N-2,6-(CH₂? C₅H₄)₂MCl₂ (M = Zr ( 2 ), Hf ( 5 )) were synthesized. The presence of N → Zr interaction favours the formation of zirconocene cations. Traces of water cause the formation of the salt-like compound [C₅H₃N-2,6-(CH₂? C₅H₄)₂Zr(Cl)(OH₂)]₂[ZrCl₆] 4 from 2 . The new compounds were characterized by ¹H n.m.r., and mass spectroscopy. The X-ray crystal structure of 4 shows discrete cations and anions which are connected by H-bridges.     

Ionenaustauschexperimente an ternären Tantalaten und Niobaten mittels Halogenidschmelzen — ein Zugang zu neuen Bleitantalaten

Exchange Reactions of Ternary Tantalates and Niobates with Halide Melts — a Way to New Lead Tantalates Ternary tantalates and niobates of the hexagonal structure-type A_(n+1)/m^m+M_3n+1O_8n+3 (A^m+ = Na⁺, Cu⁺, Ag⁺,…; M = Ta, Nb) were heated with surplus CuCl, PbCl₂, LaCl₃ or BiCl₃ (for example T = 700°C in case of PbCl₂). In some of these cases it was possible to exchange the A^m+-ions for the cations of the halide melts by maintaining the basic structure (for example: Cu₃Ta₇O₁₉ + BiCl₃ = BiTa₇O₁₉ + 3 CuCl). In different reactions the stack along the crystallographic c-axis and furthermore the proportion O/M (for example: 7 Cu₅Ta₁₁O₃₀ + 35/2 PbCl₂ = 11 Pb_1,5Ta₇O₁₉ + PbO + 35 CuCl) changed. Nevertheless, it was not possible to substitute cations of the halide melt for A^m+-ions in every direction (not possible for example: LaTa₇O₁₉ + BiCl₃). When CuCl? and PbCl₂-melt were added to Ag₂Ta₄O₁₁ and Na₂Nb₄O₁₁, these niobates showed exange reactions by changing their structure completely. If BiCl₃-melt was added, these niobates decayed while forming B? Nb₂O₅. The new hexagonal tantalates Pb_1,5Ta₇O₁₉ (a = 6,2411(7) Å; c = 19,977(3) Å) and PbTa₄O₁₁ (low-temperature modification; a = 6,2364(3) Å; c = 36,851(3) Å) were the first representatives of the structure-type A_(n+1)/m^m+M_3n+1O_8n+3 with A^m+ = Pb²⁺, which were found in a reaction with PbCl₂ (Cu₃Ta₇O₁₉ + 3/2 PbCl₂ = Pb_1,5Ta₇O₁₉ + 3 CuCl; Ag₂Ta₄O₁₁ + PbCl₂ = PbTa₄O₁₁ + 2 AgCl). These two compounds, which are probably metastable, could only be achieved by exange reactions of ions.     

Zur Koordinationschemie des 1,3-Dithiol-2-selon-4,5-diselenolats (dsise) und des 1,3-Dithiol-2-selon-4,5-dithiolats (dmise). Kristall- und Molekülstruktur des Tetrabutylammonium-bis-(1,3-dithiol-2-selon-4,5-diselenolato)nickelat(II) und -(III), [(n-C4H9)4N]2[Ni(dsise)2] und (n-C4H9)4N[Ni(dsise)2]

Coordination Chemistry of 1,3-Dithiole-2-selone-4,5-diselenolate (dsise) and 1,3-Dithiole-2-selone-4,5-dithiolate (dmise). Crystal and Molecular Structure of Tetrabutylammonium bis(1,3-dithiole-2-selone-4,5-diselenolato)nickelate(II) and -(III), [(n-C₄H₉)₄N]₂[Ni(dsise)₂ and (n-C₄H₉)₄[Ni(dsise)₂] Syntheses and properties of metal(II) and metal(III) bis-chelates of 1,3-dithiole-2-selone-4,5-diselenolate (dsise), of the general type (Bu₄N)_n)M(dsise)₂] (n =2 : M = Zn, Cd, Hg, Cu, Ni, Pd; n = 1: M = Ni, Au) are reported and compared with chelates of the isologue 1,3-dichalcogenole-2-chalcogenoe-4,5-dichalcogenolate (i. r., ¹³C-n. m. r., e. p. r., cyclovoltammetric data). The unexpected rearrangement during the syntheses of dsise and 1,3-dithiole-2-selone-4,5-diselenolate (dmise) is characterized by ab-initio SCF calculations. The x-ray structures of (Bu₄N)₂[Ni(dsise)₂] (space group P2₁/c, a = 8.5556(13) Å, b = 15.0009(12) Å, c = 19.696(3) Å, β = 96.018(7)°, V = 2513.9(5) ų, Z = 2) and Bu₄N[Ni(dsise)₂] (space group C2/c, a = 25.133(6) Å, b = 9.828(4) Å, c = 18.104(7) Å, β = 132.81(1)°, V = 3281(2) ų, Z = 4) are given.     

Substitutions- und Oxydationsreaktionen des N-Dichlorphosphanyl-triphenylphosphazens,Ph3PN?PCl2

Replacement and Oxidation Reactions of N-Dichlorophosphanyl Triphenylphosphazene, Ph₃P?N? PCl₂ The title compound ( 1 ) reacts with MeOH, EtOH, PhOH, EtSH, and water forming N-phosphanyl or N-phosphinoyl phosphazenes, resp., Ph₃P?N? PX₂ (X ? OPh( 8 ), SEt( 9 )) or Ph₃P?N? PH(O)X (X ? Cl( 3 ), OH( 4 ), OMe( 5 ), OEt( 7 )). The reaction of 1 with P(NEt₂)₃ yields Ph₃P?N? P(NEt₂)₂ ( 10 ). Ph₃P?N? PF₂( 11 ) and Ph₃P?N? PH(O)F ( 12 ) are obtained by chlorine-fluorine exchange. The N-phosphanyl compounds 1 , 8 , 9 and 11 are oxidized by NO₂ yielding the corresponding N-phosphoryl derivatives, Ph₃P?N? P(O)X₂ (X ? Cl( 2 ), OPh( 13 ), SEt ( 14 ), F( 15 )). The thiophosphoryl compounds, (Ph₃P?N? P(S)X₂ (X ? Cl( 16 ), OPh( 17 ), F( 18 )) are obtained by oxidizing 1 , 8 , and 11 with sulfur.