Beiträge zur Lanthanoidchemie. III Zur Kenntnis von 2-(Dimethylaminomethyl)ferrocenyl-Verbindungen des Samariums und Yttriums

Contribution to Organolanthanoide Chemistry. III. On 2-(Dimethylaminomethyl)ferrocenyl Compounds of Samarium and Yttrium Earlier results, indicating the ability of the bulky 2-(dimethylaminomethyl)ferrocenyl-group (FcN) to form thermocally stable, heterobimetallic organolanthanide compounds, were proved by the synthesis of organo-rare-earth derivatives (C₅Me₅)₂Sm(FcN) ( II ), (C₅H₅)Sm(FcN)Cl ( III ), respectively (C₅Me₅)Y(FcN)Cl ( IV ) from the corresponding complex cyclopentadienyl rare-earth chlorides (C₅Me₅)₂SmCl · KCl · THF, (C₅H₅)SmCl₂ · THF and (C₅Me₅)YCl₂ · KCl · 1,8 THF and 2-(dimethylaminomethyl)ferrocenyl lithium (FcN)Li ( I ) as organylating agent. The synthesized compounds were proved by elementary analysis, IR, ¹H, ¹³C NMR and UV-VIS spectra as well as by measuring the magnetic moments and by mass spectroscopy.     

Beiträge zur Lanthanoidchemie. II. Zur Kenntnis von 2-(Dimethylaminomethyl)ferrocenyl-Verbindungen des Yttriums,Dysprosiums und Holmiums

Contributions to Organolanthanide Chemistry. II. On 2-(dimethylaminomethyl)ferrocenyl Compounds of Yttrium, Dysprosium, and Holmium Early reports about the ability of the 2-(dimethylaminomethy1)ferrocenyl group to form stable heterobimetallic organolanthanide(III) compounds have been confirmed by the synthesis of the organolanthanide(III) derivatives (C₅H₅)₂Ln(FcN) [Ln = Y (II), Dy (III), Ho (IV)], C₅H₅Dy(FcN)₂ · 2,5 THF (V) und C₅H₅Ln(FcN)Cl [Ln = Dy (VI), Ho (VII)] from the corresponding cyclopentadienyllanthanide(III) chlorides (C₅H₅)₂LnCl or C₅H₅LnCl₂ resp. and (FcN)Li (I). The products have been characterized by elemental analyses, IR-, ¹H-NMR, ¹³C-NMR and UV/Vis spectra as well as mass spectra and the determination of their effective magnetic moments.     

Darstellung,Eigenschaften und Molekülstrukturen von Heterobimetallorganika des vierwertigen Germaniums mit dem 2‐(Dimethylaminomethyl)ferrocenyl‐Liganden FcN (η5‐C5H5)Fe[η5‐C5H3(CH2NMe2)‐2]

Hydrolysereak‐Syntheses, Properties and Molecular Structures of the Heterobimetalorganics of the four‐valued Germanium with the 2‐(Dimethylaminomethyl)ferrocenyl Ligand FcN (η⁵‐C₅H₅)Fe[η⁵‐C₅H₃(CH₂NMe₂)‐2] The heterobimetallic lithiumorganyl [2‐(dimethylaminomethyl)ferrocenyl] lithium, FcNLi, reacts with germanium(IV) chloride, GeCl₄, under the formation of heterobimetallic germanium(IV) organyls (FcN)_nGeCl_4‐n (n = 2 ( 1 ), 3 ( 2 )). The heterobimetallic organogermanol (FcN)₃GeOH ( 3 ) is formed at hydrolysis of 2 . A detailed characterization of the defined compounds 1 — 3 was carried out by single crystal X‐ray analyses, NMR‐ and mass‐spectrometry.     

Beiträge zur Chemie der Alkylverbindungen von Übergangsmetallen. 59. Cyclopentadienyl-2-(dimethylaminomethyl)ferrocenyl-Verbindungen elektronenarmer 3 d-Elemente

Contributions to the Chemistry of Transition Metal Alkyl Compounds. 59. Cyclopentadienyl-2-(dimethylaminomethyl)ferrocenyl Compounds of Early 3 d-Elements Compounds of the type (C₅H₅)₂M(FcN) (M = Sc ( 1 ), Ti ( 2 ), V ( 3 ), Cr ( 4 ); FcN = 2-dimethylaminomethyl)ferrocenyl group), and (C₅H₅)M(FcN)₂ (M = Ti ( 5 ), Cr ( 6 ) were synthesized and investigated. A detailled characterization with respect to the existence of chelate structures was realized by the uv-vis, ¹H-n.m.r. spectroscopic measurements and determination of magnetic moments.     

Synthesen und Charakteristika von Heterobimetallorganika des Siliciums mit dem 2‐(Dimethylaminomethyl)ferrocenyl‐Liganden FcN (η5‐C5H5)Fe[η5‐C5H3(CH2NMe2)]—

Syntheses and characteristics of the heterobimetalorganics of the silicon with the 2‐(dimethylaminomethyl)ferrocenyl ligand FcN (η⁵‐C₅H₅)Fe[η⁵‐C₅H₃(CH₂NMe₂)]^— The heterobimetallic lithiumorganyl [2‐(dimethylaminomethyl)ferrocenyl] lithium, LiFcN, reacts with silicon(IV)‐chlorid, SiCl₄, under the formation of heterobimetallic silicon(IV) organyl [(FcN)₃SiCl] ( 1 ). The heterobimetallic organosilanol [(FcN)₃SiOH] ( 2 ) is formed at hydrolysis of 1 . A detailed characterization of the defined compounds 1 and 2 was carried out by NMR‐ rsp. mass‐spectrometry and by crystal X‐ray analysis of 2 .     

Beiträge zur Chemie der Alkylverbindungen von Übergangsmetallen. 58. Zur Kenntnis von 2-(Dimethylaminomethyl)ferrocenyl-Verbindungen des Vanadiums,Molybdäns,Wolframs, Thoriums und Urans

Contributions to the Chemistry of Transition Metal Alkyl Compounds. 58 On 2-(Dimethylaminomethyl)ferrocenyl Compounds of Vanadium, Molybdenum, Tungsten, Thorium, and Uranium Earlier results according to which dimethylaminomethylferrocenyl groups (FcN) are able to form stable organometallic chelate compounds were confirmed by synthesis of the heterobimetallic chelate compounds (FcN)₂VO · Li(acac) II , (FcN)MoO₂(acac) III , (FcN)WOCl₃ IV , (FcN)Th(acac)₃ V , and (FcN)UO₂(acac) VI from the corresponding metal acetylacetonates or oxidchlorides and (FcN)Li I . The new compounds were characterized by elemental analysis, the i.r., ¹H-n.m.r., and electron spectra and by their effective magnetic moments.     

Metalloxane des Siliciums und Germaniums mit dem 2‐(Dimethylaminomethyl)ferrocenyl‐Liganden (FcN): Darstellung und Molekülstrukturen von (FcN)4M4O4(OH)4(M = Si,Ge), (FcN)6Ge6O8(OH)2 und von (FcN)2Si(OH)2

Metalloxanes of Silicon and Germanium with the 2‐(Dimethylaminomethyl)‐ferrocenyl Ligand (FcN): Synthesis and Molecular Structures of (FcN)₄M₄O₄(OH)₄(M = Si, Ge), (FcN)₆Ge₆O₈(OH)₂ and of (FcN)₂Si(OH)₂ (FcN)₄M₄O₄(OH)₄ · H₂O [FcN = 2‐(dimethylaminomethyl)ferrocenyl, M = Si ( 2 ) und Ge ( 3 )] are prepared by hydrolysis of FcNSiCl₃ or FcNGeCl₃ ( 1 ) in Et₂O in the presence of (NH₄)₂CO₃. The tricyclic compound (FcN)₆Ge₆O₈(OH)₂ ( 4 ) is formed after treatment of the hydrolysis solution of FcNGeCl₃ with CaH₂. (FcN)₂Si(OH)₂ ( 5 ) was sythesized by hydrolysis of (FcN)₂SiCl₂ under similar conditions. Compounds 1 — 5 are obtained as yellow orange crystals, the molecular structures of 1 — 5 were determinated by X‐ray diffraction. 2 and 3 are 8‐membered Si‐O/Ge‐O cycles with one OH and one FcN‐ligand on each Si or Ge atom, respectively. Compound 4 represents a stair‐like tricyclic Ge‐O structure whereas 5 is a discrete Silanediol. 2 — 5 show O‐H···N hydrogene bridges of the OH groups to the nitrogen atoms of the FcN substituents.     

Umsetzungen von Cp*NbCl4 und Cp*TaCl4 mit Trimethylsilyl‐azid,Me3Si‐N3. Molekülstrukturen der bis(azido)‐oxo‐verbrückten Komplexe [Cp*NbCl(N3)(μ‐N3)]2(μ‐O) und [Cp*TaCl2(μ‐N3)]2(μ‐O) (Cp* = Pentamethylcyclopentadienyl)

Reactions of Cp*NbCl₄ and Cp*TaCl₄ with Trimethylsilyl‐azide, Me₃Si‐N₃. Molecular Structures of the Bis(azido)‐Oxo‐Bridged Complexes [Cp*NbCl(N₃)(μ‐N₃)]₂(μ‐O) and [Cp*TaCl₂(μ‐N₃)]₂(μ‐O) (Cp* = Pentamethylcyclopentadienyl) The chloro ligands in Cp*TaCl₄ (1c) can be stepwise substituted for azido ligands by reactions with trimethylsilyl azide, Me₃Si‐N₃ (A) , to generate the complete series of the bis(azido)‐bridged dimers [Cp*TaCl_3‐n(N₃)_n(μ‐N₃)]₂ ( n = 0 (2c) , n = 1 (3c) , n = 2 (4c) and n = 3 (5c) ). If the solvent CH₂Cl₂ contains traces of water, an additional oxo bridge is incorporated to give [Cp*‐TaCl₂(μ‐N₃)]₂(μ‐O) (6c) or [Cp*TaCl(N₃)(μ‐N₃)]₂(μ‐O) (7c) , respectively. Both 6c and 7c are also formed in stoichiometric reactions from [Cp*TaCl₂(μ‐OH)]₂(μ‐O) (8c) and A . Analogous reactions of Cp*NbCl₄ (1b) with A were used to prepare the azide‐rich dinuclear products [Cp*NbCl_3‐n(N₃)_n(μ‐N₃)]₂ (n = 2 (4b) , and n = 3 (5b) ), and [Cp*NbCl(N₃)(μ‐N₃)]₂(μ‐O) (7b) . The mononuclear complex Cp*Ta(N₃)Me₃ (10c) is obtained from Cp*Ta(Cl)Me₃ and A . All azido complexes were characterised by their IR as well as their ¹H and ¹³C NMR spectra; X‐ray crystal structure analyses are available for 6c and 7b .     

Further studies of phosphine adducts of niobium(IV) and tantalum(IV) chlorides: New seven- and eight-coordinate compounds with trimethylphosphine: NbCl4(PMe3)3 and Ta2Cl8(PMe3)4

The reaction of NbCl₄(THF)₂ with an excess of PMe₃ in toluene solution afforded a 70% isolated yield of green NbCl₄(PMe₃)₃. When a slurry of TaCl₅ in toluene containing a slight excess of PMe₃ was reduced with sodium amalgam overnight, a 60% yield of orange to red (depending on crystal size) Ta₂Cl₈(PMe₃)₄ was obtained. Both compounds have been fully characterized by X-ray crystallography. NbCl₄(PMe₃)₃ forms monoclinic crystals (P2₁/c) with unit cell dimensions a = 15.061(3) Å, b = 11.677(4) Å, c = 11.583(4) Å, β = 91.71(3)°, V = 2036(2) ų, and Z = 4. It is isomorphous with its TaCl₄(PMe₃)₃ homolog, and the bond lengths and angles are very similar. Ta₂Cl₈(PMe₃)₄ forms cubic crystals (Im3) with a = 16.377(2), V = 4392(2) ų and Z = 6. It is thus isomorphous with its niobium homolog, and the internal dimensions are quite comparable. The Ta-Ta distance is 2.830(1) Å, consistent with the existence of a single bond.     

Oxo- und Thiotantal(V)-Verbindungen: Synthese von TaOX3 und TaSX3 (X = OR,SR)

Oxo- and Thiotantalum(V) Compounds: Synthesis of TaOX₃ and TaSX₃ (X = OR, SR) TaO(OR)₃ [R = ^tC₄H₉, Mes* ( 2 )], TaO(SR)₃ [R = ^tC₄H₉, p-Tolyl], TaS(OR)₃ [R = ^tC₄H₉, Mes* ( 6 )] and TaS(SR)₃ [R = ^tC₄H₉, p-Tolyl] have been prepared by reaction of TaOCl₃ and TaSCl₃ with LiOR or LiSR. The reaction of TaCl₅ with an excess of LiOMes* yields the chlorotantalum(V)compounds TaCl₃(OMes*)₂ and TaCl₂(OMes*)₃ ( 10 ). The synthesis of TaCl₂(ⁿC₄H₉)(OMes*)₂ ( 11 ), Ta(Sp-Tolyl)₅ and TaCl₂(OEt)₃ · C₅H₅N are also described. 2, 6, 10 and 11 decompose in benzolic solution or by heating under vacuum splitting off 2,4,6-tri-tert-butyl-phenol, n-butane respectively, and forming cyclometallated tantalum(V) complexes with the bidentate ligand OC₆H₂^tBu₂CMe₂CH₂. TaCl₂(OEt)₃ was investigated by X-ray diffraction analysis; the crystal structure has been found to be a binuclear tantalum complex with two bridging ethoxo ligands.     

Metallchlorid-Graphitverbindungen aus nichtwäßrigen Lösungsmitteln Einlagerung aus Thionylchloridlösungen

Metal Chloride-Graphite Compounds from Nonaqueous Solvents. Intercalation from Thionylchloride Solutions The intercalation of UCl₅, AlCl₃, NbCl₅, TaCl₅, and MoOCl₄ from SOCl₂ solutions is investigated. From concentrated UCl₅ solutions, dependent on the temperature, two compounds are obtained: UCl₅-graphite and UCl₅–SOCl₂-graphite, both with the structure of a first intercalation stage. The other metal chlorides are intercalated without SOCl₂: AlCl₃ to a second stage; NbCl₅, TaCl₅ and MoOCl₄ to a third stage. Chlorine additionally bound in the AlCl₃, NbCl₅ and TaCl₅ compounds results from a decomposition reaction of the SOCl₂.     

Phosphor‐Chalkogen‐Moleküle als Komplexliganden – Reaktionen mit NbCl5

Phosphorus Chalcogen Molecules as Complex Ligands – Reactions with NbCl₅ The reaction of P₄E₃ (E = S, Se) with NbCl₅ yields [β‐P₄S₄(NbCl₅)₂] and [P₄Se₃(NbCl₅)]. [β‐P₄S₄(NbCl₅)₂] crystallizes in the monoclinic space group P2₁/n with the lattice parameters a = 6.226(1), b = 12.971(2), c = 26.380(2) Å, β = 93.7(1) (Z = 4). In this compound a sulfur atom is introduced into the basal P₃‐ring and the resulting β‐P₄S₄ is central unit of the complex. [P₄Se₃(NbCl₅)] crystallizes in the same space group type with the lattice parameters a = 11.939(1), b = 18.603(2), c = 12.763(4) Å, β = 90.16(2)° (Z = 8). In both compounds the ligands are coordinated to basal phosphorus atoms.     

Convenient,high yield syntheses of [Nb(O)Cl3], [Nb(O)Cl3(CH3CN)2] and [NB(O)Cl3(THF)2]. Formation and decomposition of intermediate alkoxo (and siloxo) derivatives of general formula [NbCl4(OR)]2 (R = Me,Et, SiMe3)

Trimethylsilylaklylethers, Me₃SiOR (R = Me, Et) and hexamethyldisiloxane react with NbCl₅ in dichloromethane under ambient conditions to give readily isolable mono-alkoxides, [NbCl₄(OR)]₂ (R = Me, 1; Et, 2) and the thermally sensitive siloxide [NbCl₄(OSiMe ₃)]₂ (3), respectively. At 80°C in 1,2-dichloroethane, 1–3 undergo efficient conversion to [Nb(O)Cl₃] with elimination of RCl. In acetonitrile solution, the reaction of NbCl₅ with (Me₃Si)₂O proceeds smoothly to give [Nb(O)Cl₃(CH₃CN)₂] which is readily converted to [Nb(O)Cl₃(THF)₂] upon dissolution in tetrahydrofuran (THF).     

Molecular precursors for the CVD of niobium and tantalum nitride

Treatment of NbCl₅ with excess HN(SiMe₂Ph)₂ in toluene resulted in the formation of crystalline [NbCl₃(NSiMe₂Ph)(NH₂SiMe₂Ph)]₂. In the presence of excess 3,5-lutidine (3,5-Me₂C₅H₃N), the reaction of TaCl₅ with 2 equivalents of HN(SiMe₃)₂ resulted in the isolation of the monomeric complex [TaCl₃(NSiMe₃)(NC₅H₃Me₂-3,5)₂]. The X-ray crystal structure of [TaCl₃(NSiMe₃)(NC₅H₃Me₂-3,5)₂] has been determined. Low pressure chemical vapour deposition of [NbCl₃(NSiMe₂Ph)(NH₂SiMe₂Ph)]₂ and [TaCl₃(NSiMe₃)(NC₅H₃Me₂-3,5)₂] forms thin films of niobium and tantalum nitride, respectively, at 600 °C.     

Phosphaniminato-Komplexe von Niob und Tantal. Die Kristallstrukturen von [NbCl4(NPiPr3)(CH3CN)], [NbCl3(NPiPr3)2], [TaCl4(NPiPr3)]2 und [TaCl3(NPiPr3)2]

Phosphorane Iminato Complexes of Niobium and Tantalum. Crystal Structures of [NbCl₄(NPⁱPr₃)(CH₃CN)], [NbCl₃(NPⁱPr₃)₂], [TaCl₄(NPⁱPr₃)]₂, and [TaCl₃(NPⁱPr₃)₂] The title compounds have been prepared from the pentachlorides of niobium and tantalum with the silylated phosphorane imine Me₃SiNPⁱPr₃. They are characterized by IR spectroscopy and crystal structure determinations. NbCl₄(NPⁱPr₃)(CH₃CN)] . Space group Pna2₁, Z = 4, 2102 observed unique reflections, R = 0.022. Lattice dimensions at ?50°C: a = 1627.2, b = 876.3, c = 1335.3 pm. The compound forms monomeric molecules with the acetonitrile molecule in trans position to the phosphorane iminato group. This group shows a short NbN distance of 178.2 pm with a NbNP bond angle of 165.2°. [NbCl₃(NPⁱPr₃)₂] . Space group Cc, Z = 4, 2534 observed unique reflections, R = 0.046. Lattice dimensions at 20°C: a = 1302.65, b = 1321.69, c = 1672.04 pm, β = 111.713°. The compound forms monomeric molecules with a distorted bipyramidal surrounding of the niobium atom and equatorially arranged phosphorane iminato groups. [TaCl₄(NPⁱPr₃)]₂ . Space group Pbca, Z = 4, 1537 observed unique reflections, R = 0.037. Lattice dimensions at ?40°C: a = 1420.6, b = 1483.9, c = 1622.0 pm. The compound forms centrosymmetric dimeric molecules with dissimilarly long Ta₂Cl₂ bridges and equatorially arranged phosphorane iminato groups. [TaCl₃(NPⁱPr₃)₂] . Space group Cc, Z = 4, 5737 observed unique reflections, R = 0.039. Lattice dimensions at ?50°C: a = 1303.9, b = 1327.2, c = 1682.1 pm, β = 111,92°. The compound is isotypical with the corresponding niobium compound.     

Heterobimetallische Komplexe von Lithium,Aluminium und Gold mit dem N‐[2‐N′,N′‐(Dimethylaminoethyl)‐N‐methyl‐aminoethyl]‐ferrocenyl‐Liganden (η5‐C5H5)Fe{η5‐C5H3[CH(CH3)N(CH3)CH2CH2NMe2]‐2}

Heterobimetallic Complexes of Lithium, Aluminum, and Gold with the N ‐[2‐ N ′, N ′‐(dimethylaminoethyl)‐ N ‐methyl‐aminoethyl]‐ferrocenyl Ligand (η⁵‐C₅H₅)Fe{η⁵‐C₅H₃[CH(CH₃)N(CH₃)CH₂CH₂NMe₂]‐2} N‐[2‐N′,N′‐(dimethylaminoethyl)‐N‐methyl‐aminoethyl]ferrocene FcN,NH ( 1 ) reacts with ⁿBuLi under formation of the lithium organyl (FcN,N)Li ( 2 ). At reactions of 2 with AlBr₃ and AuCl · PPh₃ the heterobimetallic organo derivatives (FcN,N)AlBr₂ ( 3 ), (FcN,N)Au · PPh₃ ( 4 ) are formed. A detailed characterization of 2 – 4 was carried out by single crystal x‐ray analyses as well as by NMR and Mößbauer spectroscopy.     

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.     

Die Kristallstrukturen der Verbindungen PCl5NbCl5 und PCl5TaCl5

Crystals of PCl₅NbCl₅ and PCl₅TaCl₅ are isomorphous; space group P1 . The structures are ionic, consisting of tetrahedral cations PCl₄⁺ and octahedral anions NbCl₆^? and TaCl₆^?, respectively. Twinning is frequently observed in both compounds; an explanation thereof is given on the basis of the OD theorie.     

Nb and Ta Adducts: Connecting d0 Metal Chlorides and Phosphorus Sulfide Cages

Phosphorus sulfide cages α‐P₄S₄, α‐P₄S₅, β‐P₄S₅, and β‐P₄S₆ and transition‐metal chlorides TaCl₅ and NbCl₅ form molecular adducts in CS₂/n‐hexane. The crystal structures of the adducts (TaCl₅)(α‐P₄S₄), (TaCl₅)(α‐P₄S₅), (TaCl₅)(β‐P₄S₅), (NbCl₅)(β‐P₄S₅), and (TaCl₅)(β‐P₄S₆) are reported and their conformation and energetic stability are discussed on the basis of ab initio electronic structure calculations. Furthermore bond lengths of coordinated and noncoordinated phosphorus sulfide cages obtained from experiment and theory are compared, emphasizing the changes within the cages that emerge upon coordination.     

Zinc and aluminium trimethylsilylmethyls and their use as alkylating agents

The trimethylsilylmethyl compounds Zn(Me₃SiCH₂)₂ and Al(Me₃SiCH₂)₃(C₂H₅)₂O and some amine derivatives of the former are described. Action of the zinc alkylon NbCl₅ and TaCl₅ differs from alkylation by lithium or magnesium reagents in giving the di- or trialkyl chloro species.