Synthese und Kristallstrukturen von [Li(thf)4]2[Bi4I14(thf)2], [Li(thf)4]4[Bi5I19] und (Ph4P)4[Bi6I22]

Synthesis and Crystal Structure of [Li(thf)₄]₂[Bi₄I₁₄(thf)₂], [Li(thf)₄]₄[Bi₅I₁₉], and (Ph₄P)₄[Bi₆I₂₂] Solutions of BiI₃ in THF or methanol react with MI (M = Li, Na) to form polynuclear iodo complexes of bismuth. The syntheses and results of X-ray structure analyses of compounds [Li(thf)₄]₂[Bi₄I₁₄(thf)₂], [Li(thf)₄]₄[Bi₅I₁₉], [Na(thf)₆]₄[Bi₆I₂₂] and (Ph₄P)₄[Bi₆I₂₂] are described. The anions of these compounds consist of edge-sharing BiI₆ and BiI₅(thf) octahedra. The Bi atoms lie in a plane and are coordinated by bridging and terminal I atoms and by THF ligands in a distorted octahedral fashion. [Li(thf)₄]₂[Bi₄I₁₄(thf)₂]: Space group P1 (No. 2), a = 1 159.9(6), b = 1 364.6(7), c = 1 426.5(7) pm, α = 114.05(3), β = 90.01(3), γ = 100.62(3)°. [Li(thf)₄]₄[Bi₅I₁₉]: Space group P2₁/n (No. 14), a = 1 653.0(9), b = 4 350(4), c = 1 836.3(13) pm, β = 114.70(4)°. [Na(thf)₆]₄[Bi₆I₂₂]: Space group P2₁/n (No. 14), a = 1 636.4(3), b = 2 926.7(7), c = 1 845.8(4) pm, β = 111.42(2)°. (Ph₄P)₄[Bi₆I₂₂]: Space group P1 (No. 2), a = 1 368.6(7), b = 1 508.1(9), c = 1 684.9(8) pm, α = 98.28(4), β = 95.13(4), γ = 109.48(4)°.     

Preparation and Crystal Structure of the Neodymium Borohydride [Li(thf)4]2[Nd2(μ‐Cl)2(BH4)6(thf)2]

The neodymium borohydride [Li(thf)₄]₂[Nd₂(μ‐Cl)₂(BH₄)₆(thf)₂] was synthesized from neodymium chloride and lithium borohydride. The compound crystallized in the triclinic crystal system, space group (No. 2) with the cell constants a = 14.8613(11), b = 17.8715(13), c = 23.5846(18) Å, α = 100.760(6), β = 90.648(6) and γ = 103.294(6)°. Each neodymium atom is coordinated by three borohydride anions and a THF molecule whereas two neodymium cations are bridged through two chloro ligands. The charge of the [Nd₂(μ‐Cl)₂(BH₄)₆(thf)₂]²⁻ anion, which represents the first structurally characterized binuclear mixed borohydride chlorido complex, is compensated by two [Li(thf)₄]⁺ cations.     

Synthese und Struktur eines Molybdän–Gadolinium-Heterometall-Komplexes Die Struktur von [Li(thf)4]2[Cp2MoSGdBr4(thf)]2

Synthesis and structure of a Molybdenum–Gadolinium Heterometallic Complex. The Structure of [Li(thf)₄]₂[Cp₂MoSGdBr₄(thf)]₂ [Cp₂MoHLi] reacts in THF with S and GdBr₃ to yield the tetranuclear heterobimetallic complex [Li(thf)₄]₂[Cp₂MoSGdBr₄(thf)]₂. The bonding situation and the structure of this compound were characterized by X-ray structure analysis (space group P1 (No. 2), Z = 1, a = 10.845(2) Å, b = 12.166(2) Å, c = 15.881(2) Å, α = 101.74(2)°, β = 97.62(2)°, γ = 103.97(2)°). Each S atom of the central Mo₂S₂-ring is coordinated by a GdBr₄(thf) fragment. Additionally each Mo atom is connected to two Cp ligands. This leads to a tetrahedral coordination of the Mo atoms and a octahedral coordination of the Gd ions.     

Halide abstraction reactions of tin(IV) chloride and the group 3 chlorides MCl3 (M = Sc,Y, La) in thf: crystal and molecular structure of [ScCl2(thf)4][SnCl5(thf)]

Direct treatment (1:1) of MCl₃ (M = Sc, Y or La) with SnCl4 in thf provides colourless compounds of the type ScSnCl₇(thf)₅ and MSnCl₇(thf)₆ (M = Y, La), which have been characterised by elemental analysis and spectroscopic studies. An X-ray determination of ScSnCl₇(thf)₅ reveals an ionic structure comprising individual six-coordinate [ScCl₂(thf)₄]⁺ cations and [SnCl₅(thf)]^-anions. The cations feature an octahedral metal geometry in which a linear Cl-Sc-Cl unit is surrounded by an equatorial girdle of four solvent (thf) molecules.     

Syntheses of the Antimonides R2Sb− (R = Ph,Mes, tBu,tBu2Sb) and Sb73− by Reactions of Organoantimony Hydrides or cyclo‐(tBuSb)4 with Li,Na, K,or BuLi

Reactions of R₂SbH with BuLi at ?70 °C in tetrahydrofuran (thf) lead to [R₂SbLi(thf)₃] [R = Ph ( 1 ) or R = Mes ( 2 )]. The antimonides [tBu₂SbK(pmdeta)] ( 3 ) (pmdeta = pentamethyldiethylenetriamine), [Li(tmeda)₂][tBu₄Sb₃]·benzene ( 4 ) (tmeda = tetramethylethylenediamine), and [tBu₄Sb₃Na(tmeda, thf)] ( 5 ) result from the reduction of cyclo‐(tBuSb)₄ by Li, Na, or K with pmdeta or tmeda in thf. The primary stibanes RSbH₂ [R = Mes ( 6 ), 2‐(Me₂NCH₂)C₆H₂ ( 7 )] are synthesized by reactions of RSbCl₂ with LiAlH₄. PhSbH₂ reacts with BuLi, and tmeda in toluene to give [Sb₇Li₃(tmeda)₃]·toluene ( 8 ). [Sb₇Na₃(pmdeta)₃]·toluene ( 9 ) is obtained from PhSbH₂, Na in liqu. NH₃, pmdeta and toluene. Crystal structures are reported for 1 – 5 and 9 .     

Syntheses and X‐Ray Crystal Structures of [Li(thf)4][SnCl5(thf)] and {[Li(Et2O)2]2‐(μ‐Cl2)2‐SnIVCl2}

The syntheses and single crystal X‐ray structure determinations are reported for [Li(thf)₄][SnCl₅(thf)] ( 1 ) and {[Li(Et₂O)₂]₂‐(μ‐Cl₂)₂‐Sn^IVCl₂} ( 2 ). Compound 1 is ionic with a tetrahedral coordinated lithium cation and distorted octahedral tin (IV) atom in the anion, while compound ( 2 ) is a centrosymmetric heteronuclear double salt of LiCl and SnCl₄. [Li(thf)₄][SnCl₅(thf)] is monoclinic, P2₁/n, a = 11.204(1), b = 15.599(1), c = 17.720(2) Å; β = 96.734(2)°, Z = 4, R 0.0418; {[Li(Et₂O)₂]₂‐(μ‐Cl₂)₂‐Sn^IVCl₂} is monoclinic, P2₁/n, a = 10.848(2), b = 12.764(2), c = 11.748(2) Å; β = 90.388(3)°, Z = 4, R = 0.0851.     

Synthese und Struktur der Nitrido‐Komplexe (PPh4)2[(O3Os≡N)2MCl2](M = Pd und Pt) und [{(Me2PhP)3Cl2Re≡N}2PdCl2]

Synthesis and Structure of the Nitrido Complexes (PPh₄)₂[(O₃Os≡N)₂ MCl₂] (M = Pd und Pt) and [{(Me₂PhP)₃Cl₂Re≡N}₂PdCl₂] The threenuclear complexes (PPh₄)₂[(O₃Os≡N)₂MCl₂] (M = Pd ( 1a ) and Pt ( 1b )) are obtained by the reaction of (PPh₄) [OsO₃N] with [MCl₂(NCC₆H₅)₂] (M = Pd and Pt) in form of orange red ( 1a ) or red brown ( 1b ) crystals. The compounds crystallize isotypically in the monoclinic space group P2₁/n with a = 1052.35(6), b = 1376.70(6), c = 1607.3(1) pm, β = 94.669(7)°, and Z = 2 for 1a and a = 1053.27(7), b = 1371.6(1), c = 1615.9(1) pm, β = 94.557(7)°, and Z = 2 for 1b . In the centrosymmetric complex anions [(O₃O≡N)₂MCl₂]^2— a linear MCl₂ moiety is connected in trans arrangement with two complexes [O₃Os≡N]^— via asymmetric nitrido bridges Os≡N‐M. For the M²⁺ cations such results a square‐planar coordination MCl₂N₂. The virtually linear nitrido bridges are characterized by distances Os‐N = 167.5 pm ( 1a ) and 164.2 pm ( 1b ) as well as Pd‐N = 196.2 pm and Pt‐N = 197.8 pm. The reaction of ReNCl₂(PMe₂Ph)₃ with PdCl₂(NCC₆H₅)₂ in CH₂Cl₂ yields red crystals of the heterometallic complex [{(Me₂PhP)₃Cl₂Re≡N}₂PdCl₂] ( 2 ). It crystallizes as 2 · 2 CH₂Cl₂ in the monoclinic space group C2/c with a = 2138.3(5); b = 1260.9(3); c = 2375.6(2) pm; β = 96.09(1)° and Z = 4. In the threenuclear complex [{(Me₂PhP)₃Cl₂Re≡N}₂PdCl₂] with the symmetry C_i the coordination of the Pd²⁺ cation of the central PdCl₂ unit is completed by two nitrido bridges Re≡N‐Pd to complexes (Me₂PhP)₃Cl₂Re≡N forming a square‐planar arrangement. The distances in the linear nitrido bridges are Re‐N = 170.2 pm and Pd‐N = 197.1 pm.     

Synthese und Kristallstrukturen der heteronuklearen Nitrido‐Komplexe [(Me2PhP)3(MeCN)ClRe≡N–MCl5] mit M = Sn und Zr

Synthesis and Structures of the Dinuclear Nitrido Complexes [(Me₂PhP)₃(MeCN)ClRe≡N–MCl₅] with M = Sn and Zr The water sensitive complexes [(Me₂PhP)₃(MeCN)ClRe≡N–MCl₅] (M = Sn ( 1 ) und Zr ( 2 )) are obtained in dichloromethane from [ReNCl₂(PMe₂Ph)₃] and the acetonitrile adducts of SnCl₄ or ZrCl₄. The compounds crystallize as dichloromethane solvate isotypically with [(Me₂PhP)₃(MeCN)ClRe≡N–TiCl₅] · CH₂Cl₂ in the space group P2₁/n. From toluene crystallize monoclinic crystals of 1 · MeCN · C₇H₈. In the diamagnetic complexes 1 and 2 an anion [MCl₅]^– coordinates to the nitrido ligand of the cationic complex [ReNCl(MeCN)(PMe₂Ph)₃]⁺. The resulting nitrido bridges Re≡N–M are almost linear and asymmetric with Re–N = 169.5 pm, Sn–N = 230.1 pm and Re–N–Sn = 164.5° for 1 and Re–N = 168.4 pm, Zr–N = 237.2 pm and Re–N–Zr = 165.6° for 2 . The phosphine ligands at the Re atom are in a meridional arrangement.     

Neue Benzylkomplexe der Lanthanoiden. Darstellung und Kristallstrukturen von [(C5Me5)2Y(CH2C6H5)(thf)], [(C5Me5)2Sm(CH2C6H5)2K(thf)2]∞ und [(C5Me5)Gd(CH2C6H5)2(thf)]

New Benzyl Complexes of the Lanthanides. Synthesis and Crystal Structures of [(C₅Me₅)₂Y(CH₂C₆H₅)(thf)], [(C₅Me₅)₂Sm(CH₂C₆H₅)₂K(thf)₂]_∞, and [(C₅Me₅)Gd(CH₂C₆H₅)₂(thf)] YBr₃ reacts with potassium benzyl and [K(C₅Me₅)] in THF to give KBr and the monobenzyl compound [(C₅Me₅)₂ · Y(CH₂C₆H₅)(thf)] 1 . The analogous reaction with SmBr₃ in THF leads to the polymeric product [(C₅Me₅)₂Sm(CH₂C₆H₅)₂ ∞ K(thf)₂]_∞ 2 , with GdBr₃ to [(C₅Me₅)Gd(CH₂C₆H₅)₂(thf)] 3 . The structures of 1–3 were determined by X-ray single crystal structure analysis:

• Space group P1 , Z = 2, a = 851.2(4) pm, b = 952.7(4) pm, c = 1858.6(8) pm, α = 79.90(4)°, β = 77.35(4)°, γ = 73.30(3)°.
• Space group P1 , Z = 2, a = 903.3(2) pm, b = 1375.9(3) pm, c = 1801.1(4) pm, α = 100.92(3)°, β = 100.77°, γ = 98.25(3)°.
• Space group P2₁/n, Z = 8, a = 1458.2(5) pm, b = 927.8(3) pm, c = 3792.9(15) pm, β = 96.83(3)°.

     

Neue Komplexe der Lanthanoiden mit zweizähnigen Liganden. Die Strukturen von [(C17H17N2)GdBr2(thf)2] und [(C17H17N2)3Ln] (L = Sm,Gd)

New Complexes of the Lanthanoides with Bidentate Ligands. The Crystal Structures of [(C₁₇H₁₇N₂)GdBr₂(thf)₂] and [(C₁₇H₁₇N₂)₃Ln] (L = Sm, Gd) Reaction of [(AIP)Li] with GdBr₃ leads to a new mononuclear complex [(AIP)GdBr₂(thf)₂] 1 . In contrast to this with SmI₂ the compound [(AIP)₃Sm] 2 is build up. Such complexes are also formed with Gd(OR^*)₃ (R^* = O^tBu₂C₆H₃) and [(AIP)Li] in a 1:3 ratio, [(AIP)₃Gd] 3 . The structures of 1–3 were characterized by X-ray single crystal structure analysis ( 1 : space group Pna2₁ (No. 33), Z = 4, a = 1 972.7(9) pm, b = 984.7(5) pm, c = 1 425.0(8) pm, α = β = γ = 90°; 2 · 2 THF: space group C2/c (No. 15), Z = 8, a = 3 644.4(9) pm, b = 1 437.5(5) pm, c = 2 334.4(7) pm, β = 1 21.07(6)°; 3 : space group P2(1)/c (No. 14), Z = 4, a = 1 872.9(1) pm, b = 1 064.6(1) pm, c = 2 282.4(2) pm, β = 103.75(8)°).     

(Se4)2[Mo2O2Cl8][MCl6](M = Zr,Hf) — Tetraselenium(2+)Halometalates with two Different Anions

The reaction of Se₄[Mo₂O₂Cl₈] with Se₄[MCl₆] (M = Zr, Hf) or of Se, SeCl₄, MoOCl₄, and MCl₄ (M = Zr, Hf) at 120 °C in sealed evacuated glass ampoules gives (Se₄)₂[Mo₂O₂Cl₈][MCl₆] (M = Zr, Hf) in the form of dark‐green, air sensitive crystals in quantitative yield. The crystal structure analyses of both isotypic compounds (monoclinic, P2₁/c, Z = 2, a = 1336(2), b = 716(1), c = 1518(4) pm, β = 106.0(2)° for M = Zr; a = 1334.1(8), b = 715.03(9), c = 1518.2(3) pm, β = 106.00(2)° for M = Hf) show the presence of square‐planar Se₄²⁺, of dinuclear [Mo₂O₂Cl₈]^2—, and of almost regular octahedral [MCl₆]^2— ions. X‐ray crystallographic investigations on (Se₄)₂[Mo₂O₂Cl₈][ZrCl₆] give no hint for solid state phase transitions between —160 and 200 °C. This is in contrast to the related compounds Se₄[Mo₂O₂Cl₈] and Se₄[ZrCl₆] which both undergo phase transitions accompanied by reorientation of the cations and anions. (Se₄)₂[Mo₂O₂Cl₈][ZrCl₆] is paramagnetic and obeys the Curie‐Weiss law with a Weiss constant of —4(7) K indicating only weak interaction between the paramagnetic centres. The magnetic moment of 1.7(1) μ_B is consistent with the presence of Mo^V (d¹ configuration) and supports the ionic formula.     

Zur Reaktion von Makrozyklen mit Lanthanoiden. I. Die Struktur von [Li(thf)][(C22H22N4)2Ce] · THF

On the Reaction of Macrocycles with Lanthanoids. I. The Crystal Structure of [Li(thf)][(C₂₂H₂₂N₄)₂Ce] · THF In THF CeBr₃ forms with [(TMTAA)Li₂] the paramagnetic doubledecker complex [Li(thf)][(TMTAA)₂Ce]. The complex crystallizes with 1 Mol THF per formula unit. The structure was characterized by X-ray single crystal structure analysis (space group C2 (No. 5), z = 6, a = 1741.8(2) pm, b = 1622.1(2) pm, c = 2540.4(3) pm, β = 104.72(1)°). The sandwich-like arrangement of the heterocyclic ligands leads to a quadratic-prismatic coordination of the Ce³⁺ ion. One macrocyclic ligand is additionally coordinated by a [Li(thf)]⁺ fragment. The coordination of the Li ion is square pyramidal.     

SnCl2 als Brückenligand in [{(CO)5M}2Sn(Cl)2]2− (M = Cr,Mo, W) — Synthese,Struktur und Reaktivität

SnCl₂ as a Bridging Ligand in [{(CO)₅M}₂Sn(Cl)₂]^2? (M = Cr, Mo, W) — Synthesis, Structure, and Reactivity [{(CO)₅Cr}₂Sn(Cl)₂]^2?, 1 , may be obtained from [(CO)₅Cr]^2? or [(CO)₅CrSnCl₂ · THF] in fair yields. Alternatively, 1 is accessible by the reaction of [Cr₂(CO)₁₀]^2? with SnCl₂. This procedure may be extended to the synthesis of [{(CO)₅M}₂Sn(Cl)₂]^2? (M = Mo, 2 ; M = W, 3 ). The compounds 1–3 are crystallized as their alkalimetal (12-crown-4)₂ or [2,2,2]cryptand salts. X-ray analyses demonstrate bridging SnCl₂-moieties with M? Sn? M-angles close to 130° in each case. The relation of the bonding situation in 1–3 to the ones observed for stannylene or ?inidene”? complexes, respectively, is discussed. The transformation of 1 into the rhombododecahedral (X-ray analysis) Sn? O-cage compound [{(CO)₅CrSn}₆(μ₃-O)₄(μ₃-OH)₄], 4 , demonstrates the reactivity of the dianions 1–3 .     

Reaction of aryl azides with tris(trimethylsilyl)silyllithium: Synthesis of tmeda or thf adducts of [Li{N(Ar)Si(SiMe3)3}] and 1,4-trimethylsilyl migration from oxygen to nitrogen

Reaction of ArN₃ (Ar = Ph, p-MeC₆H₄, 1-naphthyl) with [Li{Si(SiMe₃)₃}(thf)₃] yielded lithium amides [Li{N(Ar)Si(SiMe₃)₃}L] (L = tmeda or (thf)₂). Similar treatment of o-phenylene diazide with 2 equiv. of [Li{Si(SiMe₃)₃}(thf)₃] formed dilithium diamide complex 4. Reaction between o-Me₃SiOC₆H₄N₃ and [Li{Si(SiMe₃)₃}(thf)₃] afforded, via 1,4-trimethylsilyl migration from oxygen to nitrogen, [Li{OC₆H₄{N(SiMe₃)Si(SiMe₃)₃}-2}]₂ (5). The structures of complexes 3 and 5 have been determined by single crystal X-ray diffraction techniques.     

Thiomethylmagnesium Chlorides: Synthesis via Hg–Mg Transmetallation and Crystallization of a Grignard Compound as 1/1 Adduct of [Mg(CH2SPh)2(thf)3] and [MgCl2(thf)4]

Thiomethylmercury chlorides 2 Hg(CH₂SMe)Cl · HgCl₂ and Hg(CH₂SPh)Cl react with magnesium in thf to give the Grignard compounds Mg(CH₂SR)Cl (R = Me ( 1 ), Ph ( 2 )) in nearly quantitative yields. From thf/n‐hexane solutions of 2 precipitate at –40 °C colorless crystals of the composition Mg(CH₂SPh)Cl · 3.5 thf ( 2 ′). X‐ray structure determination revealed, that the unit cell contains separated molecules of [Mg(CH₂SPh)₂(thf)₃] and [MgCl₂(thf)₄]. In the [Mg(CH₂SPh)₂(thf)₃] molecules magnesium is distorted trigonal‐bipyramidally coordinate. Two PhSCH₂ and one thf ligand occupy the equatorial positions and two further thf ligands the apical ones. In the [MgCl₂(thf)₄] molecules Mg displays an octahedral coordination with chloro ligands in mutual trans position. Temperature dependent NMR measurements of 2 reveal that in thf the Schlenk equilibrium operates; the composition of the equilibrium mixture at room temperature was estimated to be 89% Mg(CH₂SPh)Cl and 11% Mg(CH₂SPh)₂.     

Organo‐Palladium(II)‐Verbindungen mit PdC4‐Koordination: Phenylethinyl‐ und Methylphenylethinylkomplexe

Tetrakis(p‐tolyl)oxalamidinato‐bis[acetylacetonatopalladium(II)] ([Pd₂(acac)₂(oxam)]) reacted with Li–C≡C–C₆H₅ in THF with formation of [Pd(C≡C–C₆H₅)₄Li₂(thf)₄] ( 1a ). Reaction of [Pd₂(acac)₂(oxam)] with a mixture of 6 equiv. Li–C≡C–C₆H₅ and 2 equiv. LiCH₃ resulted in the formation of [Pd(CH₃)(C≡C–C₆H₅)₃Li₂(thf)₄] ( 2 ), and the dimeric complex [Pd₂(CH₃)₄(C≡C–C₆H₅)₄Li₄(thf)₆] ( 3 ) was isolated upon reaction of [Pd₂(acac)₂(oxam)] with a mixture of 4 equiv. Li–C≡C–C₆H₅ and 4 equiv. LiCH₃. 1 – 3 are extremely reactive compounds, which were isolated as white needles in good yields (60–90%). They were fully characterized by IR, ¹H‐, ¹³C‐, ⁷Li‐NMR spectroscopy, and by X‐ray crystallography of single crystals. In these compounds Li ions are bonded to the two carbon atoms of the alkinyl ligand. 1a reacted with Pd(PPh₃)₄ in the presence of oxygen to form the already known complexes trans‐[Pd(C≡C–C₆H₅)₂(PPh₃)₂] and [Pd(η²‐O₂)(PPh₃)₂]. In addition, 1a is an active catalyst for the Heck coupling reaction, but less active in the catalytic Sonogashira reaction.     

Die Struktur von [Li(tmeda)2][Zn(2,4,6-i-Pr3C6H2)3]

X-Ray Structure of [Li(tmeda)₂][Zn(2,4,6- i Pr₃C₆H₂)₃] A side reaction of zinc halide containing VCl₂(tmeda)₂ and Li(2,4,6-iPr₃C₆H₂) formed [Li(tmeda)₂][Zn(2,4,6-iPr₃C₆H₂)₃] · 0,5[(tmeda)Li(μ-Cl)]₂. The crystal structure (orthorhombic, Pbca, a = 26,226(2), b = 19,739(2), c = 27,223(5) Å, Z = 8, R = 0,062, wR² = 0,154) contains trigonal planar zinc anions with Zn–C distances of 2,039(7) Å (average) and a propeller like arrangement of the aryl rings.     

Synthesen und Strukturen der phosphor- und stickstoffverbrückten Übergangsmetallkomplexe [Pd(NPhPPh2)(PPh3)]2, [Pd(NPhPPh2)2 · Li(thf)]2, [Pd(NPhPPh2)Cl · Li(thf)3]2, [M(NPhPPh2)(HNPhPPh2)]2 (M  Pd,Pt), [M{Ph2P(NPh)2}2] (M  Co,Ni), [Ni(PPh2){Ph2P(NPh)2}]2 und [Ni2(PPh2)(NPhPPh2)(HNPhPPh2)3]

Syntheses and Structures of the Phosphorus and Nitrogenbridged Transition Metal Complexes [Pd(NPhPPh₂)(PPh₃)]₂, [Pd(NPhPPh₂)₂ · Li(thf)]₂, [Pd(NPhPPh₂)Cl · Li(thf)₃]₂, [M(NPhPPh₂)(HNPhPPh₂)]₂ (M?Pd, Pt), [M{Ph₂P(NPh)₂}₂] (M?Co, Ni), [Ni(PPh₂){Ph₂P(NPh)₂}]₂ and [Ni₂(PPh₂)(NPhPPh₂)(HNPhPPh₂)₃] . From the reaction of LiNPhPPh₂ with Palladium-Nickel- and Cobaltcomplexes, depending on the reaction conditions, different monomeric and dimeric complexes can be isolated. In these compounds the (NPhPPh₂)^?-group acts as both a bridging and as a terminal ligand. [Pd(NPhPPh₂)(PPh₃)]₂ ( 1 ), [Pd(NPhPPh₂)₂ · Li(thf)]₂ ( 2 ) and [Pd(NPhPPh₂)Cl · Li(thf)₃]₂ ( 3 ) are formed from the reaction of [PdCl₂(PPh₃)₂] or [PdCl₂(COD)] with LiNPhPPh₂. In contrast to this from the reaction of Pd(Ac)₂ and HNPhPPh₂ (in the presence of zinc-dust) or [PtCl₂(py)₂] and LiNPhPPh₂.     

Reaktionen von Lanthanoidhalogeniden mit Alkalibenzylverbindungen. Darstellung und Kristallstrukturen von [(tmeda)(C6H5CH2)2Y(μ-Br)2Li(tmeda)], [(tmeda)2SmBr(μ-Br)2Li(tmeda)] und [(dme)2SmBr(μ-Br)]2

Reactions of Lanthanide Halides with Alkalibenzyl Compounds. Synthesis and Crystal Structures of [(tmeda)(C₆H₅CH₂)₂Y(μ-Br)₂Li(tmeda)], [(tmeda)₂SmBr(μ-Br)₂Li(tmeda)] and [(dme)₂SmBr(μ-Br)]₂ Alkali-benzyl compounds react via a metathesis reaction with lanthanide halides to benzyl complexes of the rare earths. Reaction of [(C₆H₅CH₂)Li(tmeda)] with YBr₃ leads to the complex [(tmeda)Y(C₆H₅CH₂)₂ (μ-Br)₂Li(tmeda)] 1 , in which Yttrium and lithium are linked via two bromide bridges. However, the reaction of [(C₆H₅CH₂)Li(tmeda)] with SmBr₃ in toluene/tmeda leads under reduction of the Sm ion to the compound [(tmeda)₂SmBr(μ-Br)₂Li(tmeda)] 2 . 2 reacts with DME to yield the dimeric compound [(dme)₂SmBr(μ-Br)]₂ 3 . The structures of 1 – 3 were determined by X-ray single crystal structure analysis:

• 1: Space group P2₁/c, Z = 4, a = 829.5(6) pm, b = 1477.9(11) pm, c = 2575.0(10) pm, β = 92.03(6)°,
• 2: Space group P2₁, Z = 2, a = 954,7(3) pm, b = 1338.5(6) pm, c = 1244.9(5) pm, β = 107.51(3)°,
• 3: Space group P1 , Z = 1, a = 797.2(7) pm, b = 818.3(7) pm, c = 1169.7(8) pm, α = 100.96(6)°, β = 92.03(6)°, γ = 91.75(7)°.

     

Reactions of Distibanes with [Fe2(CO)9]: Synthesis,Structure and DFT Calculations of [(Et2Sb)4Fe4(CO)14], [(nPr2Sb)4Fe3(CO)10], [{(Me3SiCH2)2Sb}4Fe2(CO)6], and [2‐(Me2NCH2)C6H4SbFe2(CO)8]

The iron complexes [(Et₂Sb)₄Fe₄(CO)₁₄] ( 1 ), [(nPr₂Sb)₄Fe₃(CO)₁₀] ( 2 ), [{(Me₃SiCH₂)₂Sb}₄Fe₂(CO)₆] ( 3 ), and [2‐(Me₂NCH₂)C₆H₄SbFe₂(CO)₈] ( 4 ) were prepared by reactions of distibanes with Fe₂(CO)₉. Compounds 1 – 4 were characterized by X‐ray diffraction, ¹H NMR and IR spectroscopy as well as mass spectrometry; complex 1 was additionally characterized by density functional calculations.