Monomere Komplexe NiL mit vierzähnigen Liganden [R2P(S)N–R'–NP(S)R2]2– (= L) [1]

Monomeric Complexes NiL with Tetradentate Ligands [R₂P(S)N–R'–NP(S)R₂]^2– (= L) Metathesis of [NiCl₂(PPh₃)₂] with Li salts of the potentially tetradentate ligands [R₂P(S)N–R'–NP(S)R₂]^2– (= L) affords monomeric complexes NiL containing the chromophore NiN₂S₂ ( 1 : R = Et; a , b : R' = Me₂C–(CH₂)₂–CMe₂, o-Phenylen; 2 : R = t-Bu, R' = (CH₂)_n; a – c : n = 2, 3, 4). According to the results of magnetic measurements and VIS as well as NMR spectroscopy (¹H, ³¹P) these complexes are planar except 1 a that is tetrahedral. In case of 1 a and 2 c this was confirmed by the results of crystal structure analyses. In toluene, however, 1 a and 2 c form an equilibrium of planar (diamagnetic) and tetrahedral (paramagnetic) conformers. VT-¹H-NMR including ¹H,¹H-COSY showed a hindered Δ,Λ-inversion of 1 a below 330 K. Only with 1 b a pentacoordinate adduct 1 b · PPh₃ was obtained that completely dissociates in its components on dissolving in benzene. 1 a and 2 c crystallize in the monoclinic space group P2₁/c containing 4 molecules in the unit cell of the dimensions 1 a : a = 8.774(1), b = 12.335(2), c = 21.339(3) Å, β = 92.33(1)° and 2 c : a = 13.374(8), b = 16.197(8), c = 12.814(6) Å, β = 109.20(4)°. The coordination of the Ni atom yields in 1 a a dihedral angle ϵ of 41.7(1)° and thus a geometry intermediate between planar and tetrahedral while in 2 c the angle of 4.5(1)° reveals a nearly planar chromophore NiN₂S₂.     

Synthese und spektroskopische Charakterisierung einiger Pentacarbonylwolfram(0)‐Komplexe mit monound bicyclischen Phosphiran‐Liganden: Kristallstruktur von [{(Me3Si)2HCPC(H)H–C(H)Ph}W(CO)5]

Synthesis and Spectroscopic Characterisation of some Pentacarbonyltungsten(0) Complexes with Mono‐ and Bicyclic Phosphirane Ligands: Crystal Structure of [{(Me₃Si)₂HCPC(H)H–C(H)Ph}W(CO)₅] The tungsten(0) complex [{(Me₃Si)₂HCPC(Ph)=N}W(CO)₅] ( 1 ) reacts upon heating with alkene derivatives 2 , 6 , 8 , and 10 in toluene to form benzonitrile and the complexes [{(Me₃Si)₂HCPC(R¹,R²)–C(R³,R⁴}W(CO)₅] ( 4 , 7 a , b , 9 a , b , 11 a , b ) ( 4 (trans): R¹,R³ = Ph, R²,R⁴ = H, 7 a , b (cis, meso and rac): R¹,R³ = Ph, R²,R⁴ = H, 9 a , b (RR und SS): R¹ = Ph, R²,R³,R⁴ = H, 11 a , b : R¹=R³ = (CH₂)₄, R²,R⁴ = H). Spectroscopic and mass spectrometric data are discussed. The structure of the complex 9 a was determined by X‐ray single crystal structure analysis showing characteristic data for the phosphirane ring such as a narrow angle at phosphorus (49,2(2)°), different P–C distances (P–C(6) 182,1(5) and P–C(7) 185,2(4) pm) and 152,9(6) pm for the basal C–C bond.     

Synthese monomerer Silber(I)‐Halogenid‐Komplexe mit T‐förmigem Bau – Kristallstrukturanalyse von [P(C6H4CH2NMe2‐2)3]AgBr

Synthesis of Monomeric T‐Shaped Silver(I) Halide Complexes – Crystal Structure Analysis of [P(C₆H₄CH₂NMe₂‐2)₃]AgBr Treatment of the tetrapodal phosphane P(C₆H₄CH₂NMe₂‐2)₃ ( 1 ) with equimolar amounts of the silver(I) halides AgX ( 2 a : X = Cl, 2 b : X = Br) produces in tetrahydrofuran at 25 °C the monomeric silver(I) complexes [P(C₆H₄CH₂NMe₂‐2)₃]AgX with planar coordination at the Ag atoms ( 3 a : X = Cl, 3 b : X = Br) in excellent yields. From complex 3 b a single X‐ray crystal structure analysis was carried out. Mononuclear 3 b crystallizes in the monoclinic space group P2₁/c with the cell parameters a = 14.504(6), b = 11.034(3), c = 17.604(5) Å, β = 102.86(4)°; V = 2746.6(16) ų; Z = 4; 2953 observed unique reflections, R₁ = 0.0805. Complex 3 b consists of monomeric sub‐units with a planar T‐shaped arrangement formed by the atoms Ag1, N1, P1 as well as Br1, whereby the P1–Ag1–Br1 array is almost linear orientated.     

Einfach und doppelt deprotonierte Maleinsäure in Praseodym‐hydrogenmaleat‐octahydrat,Pr(C4O4H3)3 · 8 H2O,und Praseodym‐maleatchlorid‐tetrahydrat,Pr(C4O4H2)Cl · 4 H2O

Single and Double Deprotonated Maleic Acid in Praseodymium Hydrogenmaleate Octahydrate, Pr(C₄O₄H₃)₃ · 8 H₂O, and Praseodymiummaleatechloride Tetrahydrate, Pr(C₄O₄H₂)Cl · 4 H₂O Single crystals of Pr(C₄O₄H₃)₃ · 8 H₂O grew by slow evaporation of a solution which had been obtained by dissolving Pr(OH)₃ in aqueous maleic acid. The triclinic compound (P1, Z = 2, a = 728.63(3), b = 1040.23(3), c = 1676.05(8) pm, α = 72.108(2)°, β = 87.774(2)°, γ = 70.851(2)°, R_all = 0.0261) contains Pr³⁺ ions in ninefold coordination of oxygen atoms which belong to two monodentate maleate ions and seven H₂O molecules. There is one further non‐coordinating maleate ion and one crystal water molecule in the unit cell. Thermal treatment of Pr(C₄O₄H₃)₃ · 8 H₂O leads first to the anhydrous compound which then decomposes to the respective oxide in two steps upon further heating. Evaporation of a solution of Pr(C₄O₄H₃)₃ · 8 H₂O which contained additional Cl^– ions yielded single crystals of Pr(C₄O₄H₂)Cl · 4 H₂O. In the crystal structure (monoclinic, P2₁/c, Z = 4, a = 866.0(1), b = 1344.3(1), c = 896.9(1) pm, β = 94.48(2)°, R_all = 0.0227), the Pr³⁺ ions are surrounded by nine oxygen atoms. The latter belong to four H₂O molecules and three maleate ions. Two of the latter act as bidentate ligands.     

Die Kristallstruktur von Ph3PNBr · Br2

Crystal Structure of Ph₃PNBr · Br₂ Ph₃PNBr · Br₂ ( 1 ) has been prepared besides of other products from the reaction of Ph₃PNH with bromine, forming orange‐yellow single crystals which are characterized by IR‐spectroscopy and by a crystal structure determination. Space group P2₁/n, Z = 4, lattice dimensions at 20 °C: a = 916.76(10), b = 1351.42(8), c = 1494.9(2) pm, β = 96.191(5)°, R₁ = 0.0538. 1 has a molecular structure in which the Br₂ molecule is coordinated at the nitrogen atom of the N‐bromine‐phosphoraneimine Ph₃PNBr in a linear arrangement N–Br–Br with bond lengths N–Br of 224.5(6) pm and Br–Br of 248.4(1) pm. The nitrogen atom of 1 is ψ‐tetrahedrally coordinated in addition by the phosphorus atom with a P–N distance of 165.3(6) pm and by the covalently bonded bromine atom with a bond length of 188.9(6) pm.     

Synthese und Struktur der Phosphor-verbrückten Übergangsmetallkomplexe [Fe2(CO)6(PR)6] (R = tBu,iPr), [Fe2(CO)4(PiPr)6], [Fe2(CO)3Cl2(PtBu)5], [Co4(CO)10(PiPr)3], [Ni5(CO)10(PiPr)6] und [Ir4(C8H12)4Cl2(PPh)4]

Synthesis and Structure of the Phosphorus-bridged Transition Metal Complexes [Fe₂(CO)₆(PR)₆] (R = ^tBu, ⁱPr), [Fe₂(CO)₄(PⁱPr)₆], [Fe₂(CO)₃Cl₂(P^tBu)₅], [Co₄(CO)₁₀(PⁱPr)₃], [Ni₅(CO)₁₀(PⁱPr)₆], and [Ir₄(C₈H₁₂)₄Cl₂(PPh)₄] (P^tBu)₃ and (PⁱPr)₃ react with [Fe₂(CO)₉] to form the dinuclear complexes [Fe₂(CO)₆(PR)₆] (R = ^tBu: 1 ; ⁱPr: 2 ). 2 is also formed besides [Fe₂(CO)₄(PⁱPr)₆] ( 3 ) in the reaction of [Fe(CO)₅] with (PⁱPr)₃. When PⁱPr(P^tBu)₂ and PⁱPrCl₂ are allowed to react with [Fe₂(CO)₉] it is possible to isolate [Fe₂(CO)₃Cl₂(P^tBu)₅] ( 4 ). The reactions of (PⁱPr)₃ with [Co₂(CO)₈] and [Ni(CO)₄] lead to the tetra- and pentanuclear clusters [Co₄(CO)₁₀(PⁱPr)₃] ( 5 ), [Ni₄(CO)₁₀(PⁱPr)₆] [2] and [Ni₅(CO)₁₀(PⁱPr)₆] ( 6 ). Finally the reaction of [Ir(C₈H₁₂)Cl]₂ with K₂(PPh)₄ leads to the complex [Ir₄(C₈H₁₂)₄Cl₂(PPh)₄] ( 7 ). The structures of 1–7 were obtained by X-ray single crystal structure analysis (1: space group P2₁/c (Nr. 14), Z = 8, a = 1 758.8(16) pm, b = 3 625.6(18) pm, c = 1 202.7(7) pm, β = 90.07(3)°; 2 : space group P1 (Nr. 2), Z = 1, a = 880.0(2) pm, b = 932.3(3) pm, c = 1 073.7(2) pm, α = 79.07(2)°, β = 86.93(2)°, γ = 72.23(2)°; 3 : space group Pbca (Nr. 61), Z = 8, a = 952.6(8) pm, b = 1 787.6(12) pm, c = 3 697.2(30) pm; 4 : space group P2₁/n (Nr. 14), Z = 4, a = 968.0(4) pm, b = 3 362.5(15) pm, c = 1 051.6(3) pm, β = 109.71(2)°; 5 : space group P2₁/n (Nr. 14), Z = 4, a = 1 040.7(5) pm, b = 1 686.0(5) pm, c = 1 567.7(9) pm, β = 93.88(4)°; 6 : space group Pbca (Nr. 61), Z = 8, a = 1 904.1(8) pm, b = 1 959.9(8) pm, c = 2 309.7(9) pm. 7 : space group P1 (Nr. 2), Z = 2, a = 1 374.4(7) pm, b = 1 476.0(8) pm, c = 1 653.2(9) pm, α = 83.87(4)°, β = 88.76(4)°, γ = 88.28(4)°).     

Sterically Tuned P‐Phosphanylamino Phosphaalkenes (Me3Si)2C=PN(R)PPh2 and (iPrMe2Si)2C=PN(R)PPh2

Deprotonation of the aminophosphanes Ph₂PN(H)R 1a – 1h [R = tBu ( 1a ), 1‐adamantyl ( 1b ), iPr ( 1c ), CPh₃ ( 1d ), Ph ( 1e ), 2,4,6‐Me₃C₆H₂ (Mes) ( 1f ), 2,4,6‐tBu₃C₆H₂ (Mes*) ( 1g ), 2,6‐iPr₂C₆H₃ (DIPP) ( 1h )], followed by reactions of the phosphanylamide salts Li[Ph₂PNR] 2a , 2b , 2g , and 2h with the P‐chlorophosphaalkene (Me₃Si)₂C=PCl, and of 2a – 2g with (iPrMe₂Si)₂C=PCl, gave the isolable P‐phosphanylamino phosphaalkenes (Me₃Si)₂C=PN(R)PPh₂ 3a , 3b , 3g , and (iPrMe₂Si)₂C=PN(R)PPh₂ 4a – 4g . ³¹P NMR spectra, supported by X‐ray structure determinations, reveal that in compounds 2a , 2b , 3a , and 3b , with bulky N‐alkyl groups the Si₂C=P–N–P skeleton is non‐planar (orthogonal conformation), whereas 3g , 3h , and 4g with bulky N‐aryl groups exhibit planar conformations of the Si₂C=P–N–P skeleton. Solid 3g and 4g exhibit cisoid orientation of the planar C=P–N–C units (planar I) but in solid 3h the transoid rotamer is present (planar II). From 3g , 4d , and 4g mixtures of rotamers were detected in solution by pairs of ³¹P NMR patterns ( 3h : line broadening).     

Neue Phosphor-verbrückte Übergangsmetall-Komplexe Die Kristallstrukturen von [Co4(CO)10(PiPr)2], [Fe3(CO)9(PtBu)(PPh)], [Cp3Fe3(CO)2(PPtBu)(PtBu)], [(NiPPh3)2(PiPr)6], [(NiPPh3)Ni{(PtBu)3}2] und [Ni8(PtBu)6(PPh3)2]

New Phosphorus-bridged Transition Metal Complexes The Crystal Structures of [Co₄(CO)₁₀(PⁱPr)₂], [Fe₃(CO)₉(P^tBu)(PPh)], [Cp₃Fe₃(CO)₂(PP^tBu)· (P^tBu)], [(NiPPh₃)₂(PⁱPr)₆], [(NiPPh₃)Ni{(P^tBu)₃}₂], and [Ni₈(P^tBu)₆(PPh₃)₂] By the reaction of cyclophosphines with transition metal carbonyl-derivatives polynuclear complexes are built, in which the PR-ligands (R = organic group) are bonded in different ways to the metal. Depending on the reaction conditions the following compounds can be characterized: [Co₄(CO)₁₀ · (PⁱPr)₂] ( 2 ), [Fe₃(CO)₉(P^tBu)(PPh)] ( 3 ), [Cp₃Fe₃(CO)₂(PP^tBu) · (P^tBu)] ( 4 ), [(NiPPh₃)₂(PⁱPr)₆] ( 5 ), [(NiPPh₃)Ni{(P^tBu)₃}₂] ( 6 ) and [Ni₈(P^tBu)₆(PPh₃)₂] ( 7 ). The structures of 2–7 were obtained by X-ray single crystal structure analysis ( 2 : space group Pccn (No. 56), Z = 4, a = 1001,4(2) pm, b = 1375,1(3) pm, c = 1675,5(3) pm; 3 : space group P2₁ (No. 4), Z = 2, a = 914,3(4) pm, b = 1268,7(4) pm, c = 1028,2(5) pm, β = 101,73(2)°; 4 : space group P1 (No. 2), Z = 2, a = 946,0(5) pm, b = 1074,4(8) pm, c = 1477,7(1,0) pm, α = 107,63(5)°, β = 94,66(5)°, γ = 111,04(5)°; 5 : space group P1 (No. 2), Z = 2, a = 1213,6(2) pm, b = 1275,0(2) pm, c = 2038,8(4) pm, α = 92,810(10)°, β = 102,75(2)°, γ = 93,380(10)°; 6 : space group P1 (No. 2), Z = 2, a = 1157,5(5) pm, b = 1371,9(6) pm, c = 1827,6(10) pm; α = 69,68(3)°, β = 80,79(3)°, γ = 69,36(3)°; 7 : space group P3 (No. 147), Z = 1, a = 1114,1(2) pm, b = 1114,1(2) pm, c = 1709,4(3) pm).     

Chiral Phosphine Ligands from Amino Acids. II. A Facile Synthesis of Phosphinoserines by Nucleophilic Phosphination Reactions – X‐Ray Structure Analyses of Ar2P–CH2–CH(NHBOC)(COOMe) (Ar = Ph,m‐xylyl)

Phosphino derivatives of serine R₂P–CH₂–CH(NHBOC)(COOMe) ( 2 a – 2 d ) have been obtained in high yield by nucleophilic phosphination of N‐(tert.butoxycarbonyl)‐3‐iodo‐L‐alanine methylester with secondary phosphines R₂PH (R = Ph, 2‐tolyl, 3,5‐xylyl, cyclohexyl) in DMF using potassium carbonate as the base. Deprotection of 2 b with HCl affords the amino acid ester hydrochloride [2‐Tol₂P–CH₂–CH(NH₃)(COOMe)]⁺Cl^– ( 3 a ). The X‐ray structures of 2 a (space group P2₁/n) and 2 c (space group P 1) have been determined. The two enantiomers of 2 a or 2 c are interconnected by N–H…O hydrogen bridges forming dimers in the solid state.     

Deprotonierte Dithiocarbaminsäureester als Thiolat-S-Donor-Liganden. Strukturen von Ph(H)NC(S)SMe,Co(PhNC(S)SMe)3 und Cu6(PhNC(S)SMe)6

Deprotonated Dithiocarbamic Acid Esters as Thiolate S-Donor Ligands. Structures of Ph(H)NC(S)SMe, Co(PhNC(S)SMe)₃, and Cu₆(PhNC(S)SMe)₆ The reaction of N-phenyl-S-methyldithiocarbamate, PhN(H)C(?S)SMe, ( 1 ) with cobalt(II) and copper(II) salts yields the monomeric compound Co^III(PhNC(S)SMe)₃ ( 2 ) and the hexameric compound Cu₆^I(PhNC(S)SMe)₆ ( 3 ). These complexes contain the negatively charged imino-thiolate ligand PhN?C(? S)SMe, which has been formed by deprotonation of 1 . The crystal structures of 1 – 3 have been determined. 1 forms centrosymmetrical dimers through N? H …? S bridge bonds, the conformation in the solid state and in solution is Z,E′. Co^III shows in 2 a trigonal-antiprismatic coordination, with the ligands acting as N,S-chelates. 3 contains an octahedral Cu₆-core with Cu …? Cu-distances ranging from 276.3(5) to 305.7(4) pm. Each copper center is trigonally coordinated to one nitrogen and two sulfur atoms of three different ligands. Crystal data: 1 , triclinic, space group P1 , a = 590.5(6), b = 869.0(1), c = 968.5(9) pm, α = 67.29(8), β = 78.44(8), γ = 81.64(9)°, Z = 2, 1 775 reflections, R(R_w) = 0.0317(0.032). 2 , orthorhombic, space group Pbca, a = 978.0(2), b = 1 842.9(4), c = 3 059.7(6) pm, Z = 8, 1 129 reflections, R(R_w) = 0.0997(0.0886). 3 , monoclinic, space group P2₁/c, a = 1 363.1(3), b = 1 342.8(3), c = 1 671.9(3) pm, β = 103.48°, Z = 2, 1 374 reflections, R(R_w) = 0.0708(0.0617).     

Pr4(SeO3)2(SeO4)F6 und NaSm(SeO3)(SeO4): Selenit‐Selenate der Selten‐Erd‐Elemente

Pr₄(SeO₃)₂(SeO₄)F₆ and NaSm(SeO₃)(SeO₄): Selenite‐Selenates of Rare Earth Elements Light green single crystals of Pr₄(SeO₃)₂(SeO₄)F₆ have been obtained from the decomposition of Pr₂(SeO₄)₃ in the presence of LiF in a gold ampoule. The monoclinic compound (C2/c, Z = 4, a = 2230.5(3), b = 710.54(9), c = 835.6(1) pm, β = 98.05(2)°, R_all = 0.0341) contains two crystallographically different Pr³⁺ ions. Pr(1)³⁺ is attached by six fluoride ions and two chelating SeO₃^2– groups (CN = 10), Pr(2)³⁺ is surrounded by four fluoride ions, three monodentate SeO₃^2– and two SeO₄^2– groups. One of the latter acts as a chelating ligand, so the CN of Pr(2)³⁺ is 10. The selenite ions are themselves coordinated by five and the selenate ions by four Pr³⁺ ions. The coordination number of the F^– ions is three and four, respectively. The linkage of the coordination polyhedra leads to cavities in the crystal structure which incorporate the lone pairs of the selenite ions. The reaction of Sm₂(SeO₄)₃ and NaCl in gold ampoules yielded light yellow single crystals of NaSm(SeO₃)(SeO₄). The monoclinic compound (P2₁/c, Z = 4, a = 1066.9(2), b = 691.66(8), c = 825.88(9) pm, β = 91.00(2)°, R_all = 0.0530) contains tenfold oxygen coordinated Sm³⁺ ions. The oxygen atoms belong to five SeO₃^2– and two SeO₄^2– ions. Two of the SeO₃^2– groups as well as one of the SeO₄^2– groups act as a chelating ligand. The sodium ions are surrounded by five SeO₄^2– ions and one SeO₃^2– group. One of the selenate ions is attached chelating leading to a coordination number of seven. Each selenite group is coordinated by six (5 × Sm³⁺ and 1 × Na⁺), each selenate ion by seven cations (5 × Na⁺ and 2 × Sm³⁺).     

Facile Synthetic Access to Rhenium(II) Complexes: Activation of Carbon–Bromine Bonds by Single‐Electron Transfer

The five‐coordinated Re^I hydride complexes [Re(Br)(H)(NO)(PR₃)₂] (R=Cy 1 a , iPr 1 b ) were reacted with benzylbromide, thereby affording the 17‐electron mononuclear Re^II hydride complexes [Re(Br)₂(H)(NO)(PR₃)₂] (R=Cy 3 a , iPr 3 b ), which were characterized by EPR, cyclic voltammetry, and magnetic susceptibility measurements. In the case of dibromomethane or bromoform, the reaction of 1 afforded Re^II hydrides 3 in addition to Re^I carbene hydrides [Re(?CHR¹)(Br)(H)(NO)(PR₃)₂] (R¹=H 4 , Br 5 ; R=Cy a , iPr b ) in which the hydride ligand is positioned cis to the carbene ligand. For comparison, the dihydrogen Re^I dibromide complexes [Re(Br)₂(NO)(PR₃)₂(η²‐H₂)] (R=Cy 2 a , iPr 2 b ) were reacted with allyl‐ or benzylbromide, thereby affording the monophosphine Re^II complex salts [R₃PCH₂R′][Re(Br)₄(NO)(PR₃)] (R′=? CH?CH₂ 6 , Ph 7 ). The reduction of Re^II complexes has also been examined. Complex 3 a or 3 b can be reduced by zinc to afford 1 a or 1 b in high yield. Under catalytic conditions, this reaction enables homocoupling of benzylbromide (turnover frequency (TOF): 3 a 150, 3 b 134 h^?1) or allylbromide (TOF: 3 a 575, 3 b 562 h^?1). The reaction of 6 a and 6 b with zinc in acetonitrile affords in good yields the monophosphine Re^I complexes [Re(Br)₂(NO)(MeCN)₂(PR₃)] (R=Cy 8 a , iPr 8 b ), which showed high catalytic activity toward highly selective dehydrogenative silylation of styrenes (maximum TOF of 61 h^?1). Single‐electron transfer (SET) mechanisms were proposed for all these transformations. The molecular structures of 3 a , 6 a , 6 b , 7 a , 7 b , and 8 a were established by single‐crystal X‐ray diffraction studies.     

Synthese und Kristallstrukturen der homoleptischen Phosphaniminato‐Kationen [E(NPPh3)3]+ (E = S,Se, Te) mit Iodid und Triiodid als Gegenionen

Synthesis and Crystal Structures of the homoleptic Phosphoraneiminato Cations [E(NPPh₃)₃]⁺ (E = S, Se, Te) with Iodide and Triiodide Counter Ions N‐Iod‐triphenylphosphaneimine, INPPh₃, reacts with the chalcogenes sulfur, selenium and tellurium in boiling tetrahydrofuran to give the phosphoraneiminato complexes [E(NPPh₃)₃]⁺[¹/₂ I₃^–, ¹/₂ I^–] · THF (E = S ( 1 ), E = Se ( 2 )) and [Te(NPPh₃)₃]⁺I₃^– ( 3 ), respectively. The componds form red crystals which are characterized by IR spectroscopy and by crystal structure determinations. The homoleptic cations [E(NPPh₃)₃]⁺ have pyramidal structures with short EN and PN bond lengths, corresponding to double bonds. 1 : Space group Pa 3, Z = 8, lattice dimensions at –80 °C: a = b = c = 2192.9(1) pm, R₁ = 0.0299. 2 : Space group Pa 3, Z = 8, lattice dimensions at –80 °C: a = b = c = 2202.5(1) pm, R₁ = 0.0357. 3 : Space group Pca2₁, Z = 4, lattice dimensions at –90 °C; a = 1075.8(2); b = 1988.8(4); c = 2437.2(3) pm, R₁ = 0.0443.     

Die Kristallstrukturen einer Serie von Verbindungen mit Kationen des Typs [R3PNH2]+, [R3PN(H)SiMe3]+ und [R3PN(SiMe3)2]+

Crystal Structures of a Series of Compounds with Cations of the Type [R₃PNH₂]⁺, [R₃PN(H)SiMe₃]⁺, and [R₃PN(SiMe₃)₂]⁺ The crystal structures of a series of compounds with cations of the type [R₃PNH₂]⁺, [R₃PN(H)SiMe₃]⁺, and [R₃PN(SiMe₃)₂]⁺, in which R represents various organic residues, are determined by means of X‐ray structure analyses at single crystals. The disilylated compounds [Me₃PN(SiMe₃)₂]⁺I^–, [Et₃PN(SiMe₃)₂]⁺I^–, and [Ph₃PN(SiMe₃)₂]⁺I₃^– are prepared from the corresponding silylated phosphaneimines R₃PNSiMe₃ with Me₃SiI. [Me₃PNH₂]Cl (1): Space group P2₁/n, Z = 4, lattice dimensions at –71 °C: a = 686.6(1), b = 938.8(1), c = 1124.3(1) pm; β = 103.31(1)°; R = 0.0239. [Et₃PNH₂]Cl (2): Space group Pbca, Z = 8, lattice dimensions at –50 °C: a = 1272.0(2), b = 1147.2(2), c = 1302.0(3) pm; R = 0.0419. [Et₃PNH₂]I (3): Space group P2₁2₁2₁, Z = 4, lattice dimensions at –50 °C: a = 712.1(1), b = 1233.3(2), c = 1257.1(2) pm; R = 0.0576. [Et₃PNH₂]₂[B₁₀H₁₀] (4): Space group P2₁/n, Z = 4, lattice dimensions at –50 °C: a = 809.3(1), b = 1703.6(1), c = 1800.1(1) pm; β = 96.34(1)°; R = 0.0533. [Ph₃PNH₂]ICl₂ (5): Space group P1, Z = 2, lattice dimensions at –60 °C: a = 825.3(3), b = 1086.4(3), c = 1241.2(4) pm; α = 114.12(2)°, β = 104.50(2)°, γ = 93.21(2)°; R = 0.0644. In the compounds 1–5 the cations are connected with their anions via hydrogen bonds of the NH₂ groups with 1–3 forming zigzag chains. [Me₃PN(H)SiMe₃][O₃S–CF₃] (6): Space group P2₁/c, Z = 8, lattice dimensions at –83 °C: a = 1777.1(1), b = 1173.6(1), c = 1611.4(1) pm; β = 115.389(6)°; R = 0.0332. [Et₃PN(H)SiMe₃]I (7): Space group P2₁/n, Z = 4, lattice dimensions at –70 °C: a = 1360.2(1), b = 874.2(1), c = 1462.1(1) pm; β = 115.19(1)°; R = 0.066. In 6 and 7 the cations form ion pairs with their anions via NH … X hydrogen bonds. [Me₃PN(SiMe₃)₂]I (8): Space group P2₁/c, Z = 8, lattice dimensions at –60 °C: a = 1925.4(9), b = 1269.1(1), c = 1507.3(4); β = 111.79(3)°; R = 0.0581. [Et₃PN(SiMe₃)₂]I (9): Space group Pbcn, Z = 8, lattice dimensions at –50 °C: a = 2554.0(2), b = 1322.3(1), c = 1165.3(2) pm; R = 0.037. [Ph₃PN(SiMe₃)₂]I₃ (10): Space group P2₁, Z = 2, lattice dimensions at –50 °C: a = 947.7(1), b = 1047.6(1), c = 1601.6(4) pm; β = 105.96(1)°; R = 0.0334. 8 to 10 are built up from separated ions.     

Bis(arylimido) Molybdenum(VI) Amidinate and Guanidinate Complexes; Molecular Structures of [(ArN)2MoMe{N(Cy)C[N(i‐Pr)2]N(Cy)}] (Ar = 2,6‐i‐Pr2C6H3; Cy = Cyclohexyl) and [(2,6‐i‐Pr2C6H3N)2MoCl2] · [NH=C(C6H5)CH(SiMe3)2]

The reaction of [(ArN)₂MoCl₂] · DME (Ar = 2,6‐i‐Pr₂C₆H₃) ( 1 ) with lithium amidinates or guanidinates resulted in molybdenum(VI) complexes [(ArN)₂MoCl{N(R¹)C(R²)N(R¹)}] (R¹ = Cy (cyclohexyl), R² = Me ( 2 ); R¹ = Cy, R² = N(i‐Pr)₂ ( 3 ); R¹ = Cy, R² = N(SiMe₃)₂ ( 4 ); R¹ = SiMe₃, R² = C₆H₅ ( 5 )) with five coordinated molybdenum atoms. Methylation of these compounds was exemplified by the reactions of 2 and 3 with MeLi affording the corresponding methylates [(ArN)₂MoMe{N(R¹)C(R²)N(R¹)}] (R¹ = Cy, R² = Me ( 6 ); R¹ = Cy, R² = N(i‐Pr)₂ ( 7 )). The analogous reaction of 1 with bulky [N(SiMe₃)C(C₆H₅)C(SiMe₃)₂]Li · THF did not give the corresponding metathesis product, but a Schiff base adduct [(ArN)₂MoCl₂] · [NH=C(C₆H₅)CH(SiMe₃)₂] ( 8 ) in low yield. The molecular structures of 7 and 8 are established by the X‐ray single crystal structural analysis.     

Synthese und Kristallstruktur von Y(HSO4)3-I und Y(HSO4)3 · H2O

Syntheses and Crystal Structures of Y(HSO₄)₃-I and Y(HSO₄)₃ · H₂O Lath shaped crystals of Y(HSO₄)-I are obtained by treatment of Y₂O₃ with conc. sulfuric acid at 200 °C. Y(HSO₄)₃-I crystallizes orthorhombic (Pbca, Z = 8, a = 1201.5(1), b = 953.76(8), c = 1650.4(1) pm, R_all = 0.0388). In the crystal structure Y³⁺ is coordinated by eight monodentate HSO₄^– groups. Colorless, plate like single crystals of Y(HSO₄)₃ · H₂O grew from a solution of Y₂O₃ in 85% sulfuric acid upon cooling. In the crystal structure of the triclinic compound (P1, Z = 2, a = 679.8(1), b = 802.8(2), c = 965.9(2) pm, α = 79.99(2)°, β = 77.32(2)°, γ = 77.50(2)°, R_all = 0.0264) Y³⁺ is surrounded by seven HSO₄^– groups and one molecule of water.     

Darstellung und Eigenschaften von tetragonalen α-Di(phthalocyaninato(1−))-praseodym(III)-polyhalogeniden; Kristallstruktur von α-[Pr(Pc−)2]Br1,5

Preparation and Properties of Tetragonal α-Di(phthalocyaninato(1?))praseodymium(III)-polyhalides; Crystal Structure of α-[Pr(Pc^?)₂]Br_1.5 Brown red di(phthalocyaninato(1?))-praseodym(III)-polyhalides [Pr(Pc^?)₂]X_y (X = Br, I) of variable composition (1 ≤ y ≤ 2.5) are formed by (electro)chemical oxidation of [Pr(Pc^2?)₂]^?. The thermical decomposition of these polyhalides at 250°C yields partially oxidized, green α-[PrPc^?Pc^2?]. Due to strong spin–spin coupling of the phthalocyanin-π-radicals only Pr^III contributes to the magnetic moment of ca. 3.0 B.M. for all complexes. Green metallic prisms of [Pr(Pc^?)₂]Br_1.5 crystallize in the tetragonal α-modification: space group P4/nnc with a = 19.634(5) Å, c = 6.485(2) Å; Z = 2. In the sandwich complex Pr^III is eightfold coordinated by the isoindoline N-atoms of the two staggered (41°), nearly planar Pc^?- ligands. The quasi-onedimensional character of the structure along [001] is due to the infinite columns of Pc^? ligands. The superperiod along [001] is a consequence of the distribution of the Pr atoms onto two incompletely filled crystallographic positions at a distance of c/2 and the disordered chains of the bromine atoms extending in the same direction. Powder diffractograms of Pr(Pc )₂Br2, [Pr(Pc^?)₂]I₂ und [PrPc Pc^2?] confirm the tetragonal α-modification of these complexes, too. The content of tribromide correlates with the population of the Pr(2)-site. In the UV-VIS-NTR absorption spectrum of a thin film of Pr(Pc )₂Br, the intense bands at 13.9 and 19.5 kK are assigned to the B and Q transition, respectively. The D band at 9. kK is characteristic for isolated dimeric Pc^?-π-radicals. Due to increasing electron delocalisation as a result of the growing columns the D band is shifted to lower energy appearing successively at 6.05 and 3.3 kK. The mir and resonance Raman (RR) spectra of α-[Pr(Pr^?)₂]X_y, (X = Br, I) show the well known diagnostic bands for Pc^?-π-radicals. Thc RR spectrum of the polyiodide is dominated by the overtone progression of the totally symmetric (I-I) stretching vibration of the triiodide at 108cm^?1. The FT-Raman spectra are also marked by the totally symmetric stretching vibration of the polyhalides (Br₃ : 145cm ¹; 1₃^?:105cm^?1; I₅^? 151 cm^?1).     

K2Br(OH) und Rb2Br(OH): Zwei neue ternäre Alkalimetallhalogenidhydroxide mit ausgeprägter Strukturverwandtschaft zu KOH bzw. RbOH

K₂Br(OH) and Rb₂Br(OH): Two New Ternary Alkali Metal Halide Hydroxides with a Pronounced Structural Relationship to KOH resp. RbOH Two isotypic compounds K₂Br(OH) and Rb₂Br(OH) were prepared in the systems KOH/KBr and RbOH/RbBr. Their structures were determined by single crystal X-ray methods: K₂Br(OH): P2₁/m, Z = 2, a = 6.724(1) Å, b = 4.272(4) Å, c = 8.442(2) Å, β = 108.14(2)°, Z(F_o) = 651 with (F_o)² ≥ 3σ(F_o)², Z(parameter) = 28, R/R_w = 0.041/0.047 Rb₂Br(OH): P2₁/m, Z = 2, a = 6.918(3) Å, b = 4.483(2) Å, c = 8.850(5) Å, β = 108.08(6)°, Z(F_o) = 326 mit (F_o)² ≥ 3σ(F_o)², Z(parameter) = 27, R/R_w = 0.074/0.082. The compounds are built up by chains of [M₂(OH)⁺] connected via Br^?. The structure of the chains as well as their orientation to one another show a pronounced relationship to the structures of the room temperature modifications of the isotypic binary hydroxides KOH and RbOH.     

Darstellung der Halogeno-Pyridin-Rhenate(III), [ReX6−n (Py)n](3−n)− (X = Br,Cl; n = 1−3), sowie Kristallstrukturen von trans-[(C4H9)4N][ReBr4(Py)2], mer-[ReCl3(Py)3] und mer-[ReBr3(Py)3]

Preparation of Halogeno Pyridine Rhenates(III), [ReX_6?n(Py)_n]^(3?n)? (X = Br, Cl; n = 1?3) Crystal Structures of trans-[(C₄H₉)₄N][ReBr₄(Py)₂], mer-[ReCl₃(Py)₃], and mer- [ReBr₃(Py)₃] The mixed halogeno-pyridine-rhenates(III), [ReX_6?n(Py)_n]^(3?n)? (X = Br, Cl), n = 1?3, have been prepared for the first time by reaction of the tetrabutylammoniumsalts (TBA)₂[ReX₆] (X = Br, Cl) in pyridine with (TBA)BH₄ and separation by chromatography on Al₂O₃. Apart from the monopyridine complexes only the trans and mer isomers are formed from the bis-and tris-pyridine compounds. The X-ray structure determinations of the isotypic neutral complexes mer- [ReX₃(Py)₃] (monoclinic, space group P 2₁/n, Z = 4; for X = Cl: a = 9,1120(8), b = 12,5156(14), c = 15,6100(13) Å, β = 91,385(7)°; for X = Br: a = 9,152(5), b = 12,852(13), c = 15,669(2) Å, β = 90,43(2)°) reveal, due to the stronger trans influence of pyridine compared with Cl and Br, that the Re? X distances in asymmetric Py? Re? X3 axes with ReCl3 = 2,397 Å and ReBr3 = 2,534 Å are elongated by 1,3 and 1% in comparison with symmetric X1? Re? X2 axes with ReCl1 = ReCl2 = 2,367 Å and ReBr1 = 2,513 and ReBr2 = 2,506 Å, respectively. The Re? N bond lengths are roughly equal with 2,12 Å. Trans-(TBA)[ReBr₄(Py)₂] crystallizes triclinic, space group P1 , a = 9,2048(12), b = 12,0792(11), c = 15,525(2) Å, α = 95,239(10), β = 94,193(11), γ = 106,153(9)°, Z = 2. The unit cell contains two independent but very similar complex anions with approximate D_2h(mmm) point symmetry.     

Die Reaktionen von tBu2P–P=P(Me)tBu2 und (Me3Si)tBuP–P=P(Me)tBu2 mit PR3

The Reactions of ^tBu₂P–P=P(Me)^tBu₂ and (Me₃Si)^tBuP–P=P(Me)^tBu₂ with PR₃ ^tBu₂P–P=P(Me)^tBu₂ ( 1 ) reacts at 20 °C with PMe₃, PEt₃, P(c‐Hex)₃, P(p‐Tol)₃, PPh₂Me, PPh₂Et, PPhEt₂, PPh₂ⁱPr, PPh₃ and P(NEt₂)₃ yielding ^tBu₂P–P=PR₃ and ^tBu₂PMe; however, P^tBu₃, P^tBu₂(SiMe₃) and ^tBu₂PCl don't. ^tBu₂PH and 1 form ^tBu₂P–PH–P^tBu₂ which yields ^tBu₂P–P=PEt₃ when treated with PEt₃. Ph₂PH, ^tBuPH₂, PH₃, Ph₂PCl and EtOH don't substitute the ^tBu₂PMe group in 1 , instead, the molecule is decomposed. With PEt₃, (Me₃Si)^tBuP–P=P(Me)^tBu₂ forms (Me₃Si)^tBuP–P=PEt₃. The compounds ^tBu₂P–P=PR₃ decompose at 20 °C to different degrees giving P‐rich consecutive products of the phosphinophosphinidene.