Darstellung und Eigenschaften von (Acido)(pyridin)phthalocyaninato(2–)ruthenaten(II); Kristallstruktur von Tetra(n-butyl)ammonium(cyano)(pyridin)phthalocyaninato(2–)ruthenat(II)

Syntheses and Properties of (Acido)(pyridine)phthalocyaninato(2–)ruthenates(II); Crystal Structure of Tetra(n-butyl)ammonium (Cyano)(pyridine)phthalocyaninato(2–)ruthenate(II) Bis(tetra(n-butyl)ammonium bis(acido)phthalocyaninato(2–)ruthenate(II) reacts in boiling pyridine to yield blue purple, diamagnetic tetra(n-butyl)ammonium (acido)(pyridine)phthalocyaninato(2–)ruthenate(II), (ⁿBu₄N)[Ru(X)(py)pc^2–] (X = CN, N₃, NCS, NCO, NO₂). (ⁿBu₄N)[Ru(CN)(py)pc^2–] crystallizes in the orthorhombic space group Pca2₁ (no. 29) with cell parameters a = 28.319(5) Å, b = 29.850(3) Å, c = 24.566(7) Å, Z = 16, with four crystallographically independent complex anions present in the unit cell. Each Ru atom is located outside the centre (Ct) of the corresponding (N_iso)₄ plane (N_iso: isoindoline N atom) and coordinates axially pyridine and cyanide in a mutual trans position. The largest vertical displacement of the Ru atom from the (N_iso)₄ plane towards cyanide (d(Ru–Ct)) is 0.020 Å. The Ru–N_iso distance varies from 1.947(2) to 1.992(2) Å. The average Ru–C and Ru–N_py distance is 2.00 Å and 2.19 Å, respectively. The pc^2– ligand ist slightly distorted towards the cyanide. The cyclic and differential pulse voltammograms of (ⁿBu₄N)[Ru(X)(py)pc^2–] exhibit the first quasi-reversible one electron process (in V) at 0.46 (X = CN), 0.34 (N₃), 0.40 (NCO), 0.47 (NO₂), 0.50 V (NCS) and the second, independent of X, at approximately 1.05 V. The first process is metal directed, the second ring directed. The electronic absorption spectra and the vibrational spectra of (ⁿBu₄N)[Ru(X)(py)pc^2–] are discussed.     

Mononitrosyl‐ und trans‐Dinitrosyl‐Komplexe von Phthalocyaninaten des Mangans und Rheniums

Mononitrosyl and trans ‐Dinitrosyl Complexes of Phthalocyaninates of Manganese and Rhenium Tetra(n‐butyl)ammonium or di(triphenylphosphane)iminium nitrosylacidophthalocyaninato(2–)manganate, (cat)[Mn(NO)(X)pc^2–] (X = ONO, NCO, N₃; cat = ⁿBu₄N, PNP) is prepared from acidophthalocyaninato(2–)manganese, [Mn(X)pc^2–], (cat)NO₂ and (ⁿBu₄N)BH₄ in CH₂Cl₂ or from nitrosylphthalocyaninato(2–)manganese, [Mn(NO)pc^2–] and (ⁿBu₄N)X (X = ONO, NCO, N₃, NCS) at T < 120 °C, respectively. [Mn(NO)(X)pc^2–]^– dissociates in methanol, and [Mn(NO)pc^2–] precipitates. Nitrito(O)phthalocyaninato(2–)manganese, (cat)NO₂ and hydrogensulfide yield trans‐di(nitrosyl)phthalocyaninato(2–)manganate, ^trans[Mn(NO)₂pc^2–]^–, isolated as red violet (PNP) and (ⁿBu₄N) complex salt. Nitrosyl(triphenylphosphane oxide)phthalocyaninato(2–)manganese, [Mn(NO)(OPPh₃)pc^2–] is obtained by addition of OPPh₃ to [Mn(NO)pc^2–] at 200 °C. Di(triphenylphosphane)phthalocyaninato(2–)rhenium(II) and (PNP)NO₂ in CH₂Cl₂ or in molten (PNP)NO₂ and PPh₃ at 100 °C yields green blue l‐di(triphenylphosphane)iminium nitrosylnitrito(O)phthalocyaninato(2–)rhenate, ^l(PNP)[Re(NO)(ONO)pc^2–]. Similarly, but with (ⁿBu₄N)NO₂ red plates of tetra‐(n‐butyl)ammonium trans‐di(nitrosyl)phthalocyaninato(2–)rhenate, (ⁿBu₄N)^trans[Re(NO)₂pc^2–] is isolated. Addition of (PNP)Br or (PNP)PF₆ to a concentrated solution of (ⁿBu₄N)^trans[Re(NO)₂pc^2–] in pyridine precipitates ^l(PNP)^trans[Re(NO)₂pc^2–]. (ⁿBu₄N)^trans[Re(NO)₂pc^2–] and PPh₃ at 300 °C yield blue green nitrosyl(triphenylphosphane oxide)phthalocyaninato(2–)‐ rhenium, [Re(NO)(OPPh₃)pc^2–], that is oxidised with iodine precipitating nitrosyl(triphenylphosphane oxide)phthalocyaninato(2–)rhenium triiodide, [Re(NO)(OPPh₃)pc^2–]I₃. The crystal structures of ^l(PNP)[Mn(NO)(ONO)pc^2–] ( 1 ), ^l(PNP)‐ [Mn(NO)(NCO)pc^2–] ( 2 ), ^l(PNP)^trans[Mn(NO)₂pc^2–] ( 3 ), ^l(PNP)^trans[Re(NO)₂pc^2–] ( 4 ) [Mn(NO)(OPPh₃)pc^2–] ( 5 ), [Re(NO)(OPPh₃)pc^2–] ( 6 ), and [Re(NO)(OPPh₃)pc^2–]I₃ · CH₂Cl₂ ( 7 ) have been determined. The M–N(NO) distance varies between 1.623(12) Å in 5 and 1.846(3) Å in 3 . The M–N–O moiety is almost linear. The UV‐Vis spectra with the B band at ca. 14500 cm^–1and the Q band at 30400 cm^–1 do not dependent significantly on the axial ligand and the metal atom and its oxidation state. N–O stretching vibrations are observed in the IR spectra between 1701 cm^–1 in 3 and 1753 cm^–1 in [Mn(NO)pc^2–] or for the Re series between 1571 cm^–1 in 4 and 1724 cm^–1 in 7 . M–N(NO) stretching and M–N–O deformation vibrations are assigned in the IR spectra and resonance Raman spectra between 486 cm^–1 in 4 and 620 cm^–1 in 1 .     

Kristallstrukturen,spektroskopische Charakterisierung und Normalkoordinatenanalyse von (n‐Bu4N)2[M(ECN)4] (M = Pd,Pt; E = S,Se)

Crystal Structures, Spectroscopic Analysis, and Normal Coordinate Analysis of ( n ‐Bu₄N)₂[M(ECN)₄] (M = Pd, Pt; E = S, Se) The reaction of (NH₄)₂[PdCl₄] or K₂[PtCl₄] with KSCN or KSeCN in aqueous solutions yields the complex anions [Pd(SCN)₄]^2–, [Pt(SCN)₄]^2– and [Pt(SeCN)₄]^2–, which are converted into (n‐Bu₄N) salts with (n‐Bu₄N)HSO₄. (n‐Bu₄N)₂[Pd(SeCN)₄] is formed by treatment of (n‐Bu₄N)₂[PdCl₄] with (n‐Bu₄N)SeCN in acetone. X‐ray structure determinations on single crystals of (n‐Bu₄N)₂[Pd(SCN)₄] (monoclinic, space group P2₁/n, a = 13.088(3), b = 12.481(2), c = 13.574(3) Å, β = 91.494(15)°, Z = 2), (n‐Bu₄N)₂[Pd(SeCN)₄] (monoclinic, space group P2₁/n, a = 13.171(2), b = 12.644(2), c = 13.560(2) Å, β = 91.430(11)°, Z = 2) and (n‐Bu₄N)₂[Pt(SeCN)₄] (monoclinic, space group P2₁/n, a = 13.167(2), b = 12.641(1), c = 13.563(2) Å, β = 91.516(18)°, Z = 2) reveal, that the compounds crystallize isotypically and the complex anions are centrosymmetric and approximate planar. In the Raman spectra the metal ligand stretching modes of (n‐Bu₄N)₂[Pd(SCN)₄] ( 1 ) and (n‐Bu₄N)₂[Pt(SCN)₄] ( 3 ) are observed in the range of 260–303 cm^–1 and of (n‐Bu₄N)₂[Pd(SeCN)₄] ( 2 ) and (n‐Bu₄N)₂[Pt(SeCN)₄] ( 4 ) in the range of 171–195 cm^–1. The IR and Raman spectra are assigned by normal coordinate analysis using the molecular parameters of the X‐ray determination. The valence force constants are f_d(PdS) = 1.17, f_d(PdSe) = 1.17, f_d(PtS) = 1.44 and f_d(PtSe) = 1.42 mdyn/Å. The ⁷⁷Se NMR resonances are 23 for 2 , –3 for 4 and the ¹⁹⁵Pt NMR resonances 549 for 3 and 130 ppm for 4 .     

Darstellung,Kristallstrukturen, Schwingungsspektren und Normalkoordinatenanalysen der Tetrahalogeno‐bis‐Pyridin‐Osmium(III)‐Komplexe cis‐(n‐Bu4N)[OsCl4Py2] und trans‐(n‐Bu4N)[OsX4Py2], X = Cl,Br

Synthesis, Crystal Structures, Vibrational Spectra, and Normal Coordinate Analyses of the Tetrahalogeno‐bis‐Pyridine‐Osmium(III) Complexes cis ‐( n ‐Bu₄N)[OsCl₄Py₂] and trans ‐( n ‐Bu₄N)[OsX₄Py₂], X = Cl, Br By reaction of (n‐Bu₄N)₂[OsX₆], X = Cl, Br, with pyridine and (n‐Bu₄N)[BH₄] tetrahalogeno‐bis‐pyridine‐osmium(III) complexes are formed and purified by chromatography. X‐ray structure determinations on single crystals have been performed of cis‐(n‐Bu₄N)[OsCl₄Py₂] ( 1 ) (triclinic, space group P1, a = 9.4047(9), b = 10.8424(18), c = 17.007(2) Å, α = 71.833(2), β = 81.249(10), γ = 67.209(12)°, Z = 2), trans‐(n‐Bu₄N)[OsCl₄Py₂] ( 2 ) (orthorhombic, space group P2₁2₁2₁, a = 8.7709(12), b = 20.551(4), c = 17.174(4) Å, Z = 4) and trans‐(n‐Bu₄N)[OsBr₄Py₂] ( 3 ) (triclinic, space group P1, a = 9.132(3), b = 12.053(3), c = 15.398(2) Å, α = 95.551(18), β = 94.12(2), γ = 106.529(19)°, Z = 2). Based on the molecular parameters of the X‐ray structure determinations and assuming C₂ point symmetry for the anion of 1 and D_2h point symmetry for the anions of 2 and 3 the IR and Raman spectra are assigned by normal coordinate analysis. The valence force constants of 1 are in the Cl–Os–Cl axis f_d(OsCl) = 1.58, in the asymmetrically coordinated N′–Os–Cl ^· axes f_d(OsCl ^· ) = 1.45, f_d(OsN′) = 2.48, of 2 f_d(OsCl) = 1.62, f_d(OsN) = 2.42 and of 3 f_d(OsBr) = 1.39 and f_d(OsN) = 2.34 mdyn/Å.     

Synthese und Eigenschaften von cis-Diacidophthalocyaninato(2–)thallaten(III); Kristallstruktur von Tetra(n-butyl)ammonium-cisdinitrito(O,O′)- und -cis-dichlorophthalocyaninato(2–)thallat(III)

Syntheses and Properties of cis -Diacidophthalocyaninato(2–)thallates(III); Crystal Structure of Tetra(n-butyl)ammonium cis -dinitrito(O,O ′)- and cis -dichlorophthalocyaninato(2–)thallate(III) Blue green cis-diacidophthalocyaninato(2–)thallate(III), ^cis[Tl(X)₂pc^2–]^– (X = Cl, ONO′, NCO) is prepared from iodophthalocyaninato(2–)thallium(III) and the corresponding tetra(n-butyl)ammonium salt, (ⁿBu₄N)X in dichloromethane, and isolated as (ⁿBu₄N)^cis[Tl(X)₂pc^2–]. (ⁿBu₄N)^cis[Tl(ONO′)₂pc^2–] ( 1 ) and (ⁿBu₄N)^cis[Tl(X)₂pc^2–] · 0,5 (C₂H₅)₂O ( 2 ) crystallize in the monoclinic space group P2₁/n with cell parameters for 1: a = 14.496(2) Å, b = 17.293(5) Å, c = 18.293(2) Å, β = 98.76(1)° resp. for 2 : a = 13.146(1) Å, b = 14.204(5) Å, c = 24.900(3) Å, β = 93.88(1)°; Z = 4. In 1 , the octa-coordinated Tl atom is surrounded by four isoindole-N atoms (N_iso) and four O atoms of the bidental nitrito(O,O′) ligands in a distorted antiprism. The Tl–N_iso distances vary between 2.257(3) and 2.312(3) Å, the Tl–O distances between 2.408(3) and 2.562(3) Å. In 2 , the hexa-coordinated Tl atom ligates four N_iso atoms and two Cl atoms in a typical cis-arrangement. The average Tl–N_iso distance is 2.276 Å, the average Tl–Cl distance is 2.550 Å. In 1 and 2 , the Tl atom is directed out of the centre of the (N_iso)₄ plane (Ct_N) towards the acido ligands (d(Tl–Ct_N) = 1.144(1) Å in 1 , 1.116(2) Å in 2 ), and the phthalocyaninato ligand is concavely distorted. The vertical displacements of the periphereal C atoms amounts up to 0.82 Å. The optical and vibrational spectra as well as the electrochemical properties are discussed.     

C–H-Aktivierung: Synthese und Eigenschaften von Acetonato(C)acidophthalocyaninato(2–)metallaten(III) von Rhodium und Iridium; Kristallstruktur von Tetra(n-butyl)ammoniumacetonato(C)-azidophthalocyaninato(2–)iridat(III)

C–H-Activation: Syntheses and Properties of Acetonato( C )-acidophthalocyaninato(2–)metallates(III) of Rhodium and Iridium; Crystal Structure of Tetra(n-butyl)ammonium Acetonato( C )azidophthalocyaninato(2–)iridate(III) Phthalocyaninato(2–)metallate(I) of rhodium and iridium reacts with carbonyl substrates like acetone or acetylacetone and halides or pseudohalides forming acetonato(C)- or acetylacetonato(C)acidophthalocyaninato(2–)metallates(III), that are isolated as tetra(n-butyl)ammonium complex salts (ⁿBu₄N)[M(R)(X)pc^2–] (M = Rh, Ir; R = aC, acaC; X = Cl, I, N₃, SCN/NCS). (ⁿBu₄N)[Ir(aC)(N₃)pc^2–] · 0,25(C₂H₅)₂O · 0,5 CH₂Cl₂ crystallizes in the triclinic space group P1 with cell parameters a = 16.267(8) Å, b = 17.938(3) Å, c = 18.335(4) Å, α = 74.77(2)°, β = 73.73(3)°, γ = 84.25(3)°, V = 4954(3) ų, Z = 4. There are two crystallographically independent anions, differing by the orientation of the azido ligand either towards an isoindole group or a N_aza bridge of the phthalocyaninate, while the σ-C bonded acetonate is always oriented towards an isoindole group (gauche and ecliptical configuration). The Ir–C distances are 2.12(1) and 2.14(1) Å. Due to the trans influence of the acetonate-C atom the Ir-azide-N distances of 2.22(1)/2.24(1) Å are longer than expected. The electrochemical properties and the optical, vibrational, and ¹H-NMR spectra are discussed.     

Darstellung und Eigenschaften von Tetra(n-butyl)ammonium-cis-trifluorophthalocyaninato(2–)zirconat(IV) und -hafnat(IV); Kristallstruktur von (nBu4N)cis[Hf(F)3pc2–]

Preparation and Properties of Tetra(n-butyl)ammonium cis -Trifluorophthalocyaninato(2–)zirconate(IV) and -hafnate(IV); Crystal Structure of (ⁿBu₄N) ^cis [Hf(F)₃pc^2–] cis-Dichlorophthalocyaninato(2–)metal(IV) of zirconium and hafnium reacts with excess tetra(n-butyl)-ammoniumfluoride trihydrate to yield tetra(n-butyl)-ammonium cis-trifluorophthalocyaninato(2–)metalate(IV), (ⁿBu₄N)^cis[M(F)₃pc^2–] (M = Zr, Hf). (ⁿBu₄N)^cis[Hf(F)₃pc^2–] crystallizes in the monoclinic space group P2₁/n (# 14) with cell parameters a = 13.517(1) Å, b = 13.856(1) Å, c = 23.384(2) Å, α = 92.67(1)°, Z = 4. The Hf atom is in a ”︁square base-trigonal cap”︁”︁ polyhedron, coordinating three fluorine atoms and four isoindole nitrogen atoms (N_iso). The Hf atom is sandwiched between the (N_iso)₄ and F₃ planes (d(Hf–Ct_N) = 1.218(3) Å; d(Hf–Ct_F) = 1.229(3) Å; Ct_N/F: centre of the (N_iso)₄, respectively F₃ plane). The average Hf–N_iso and Hf–F distances are 2.298 and 1.964 Å, respectively, the average F–Hf–F angle is 84.9°. The pc^2– ligand is concavely distorted. The optical spectra show the typical metal independent π-π* transitions of the pc^2– ligand at c. 14700 and 29000 cm^–1. In the FIR/MIR spectra vibrations of the MF₃ skeleton are detected at 545, 489, 274 cm^–1 (M = Zr) and 536, 484, 263 cm^–1 (M = Hf), respectively.     

Benzeneselenolates of Mercury(II). Crystal and Molecular Structures of [Hg(SePh)2] and (Bu4N)[Hg(SePh)3]

The reaction of dibenzenediselenide, (SePh)₂, with mercury in refluxing xylene gives bis(benzeneselenolato)mercury(II), [Hg(SePh)₂], in a good yield. (ⁿBu₄N)[Hg(SePh)₃] is obtained by the reaction of [Hg(SePh)₂] with a solution of [SePh]^– and (ⁿBu₄N)Br in ethanol. The solid state structures of both compounds have been determined by X-ray diffraction. The mercury atom in [Hg(SePh)₂] (space group C2, a = 7.428(2), b = 5.670(1), c = 14.796(4) Å, β = 103.60(1)°) is linearly co-ordinated by two selenium atoms (Hg–Se = 2.471(2) Å, Se–Hg–Se = 178.0(3)°). Additional weak interactions between the metal and selenium atoms of neighbouring molecules (Hg…Se = 3.4–3.6 Å) associate the [Hg(SePh)₂] units to layers. The crystal structure of (ⁿBu₄N)[Hg(SePh)₃] (space group P2₁/c, a = 9.741(1), b = 17.334(1), c = 21.785(1) Å, β = 95.27(5)°) consists of discrete complex anions and (ⁿBu₄N)⁺ counter ions. The coordination geometry of mercury is distorted trigonal-planar with Hg–Se distances ranging between 2.5 and 2.6 Å.     

Darstellung,Kristallstrukturen und Schwingungsspektren von [Pt(N3)6]2– und [Pt(N3)Cl5]2–, 195Pt‐ und 15N‐NMR‐Spektren von [Pt(N3)nCl6–n]2– und [Pt(15NN2)n(N215N)6–n]2–, n = 0–6

Synthesis, Crystal Structures, and Vibrational Spectra of [Pt(N₃)₆]^2– and [Pt(N₃)Cl₅]^2–, ¹⁹⁵Pt and ¹⁵N NMR Spectra of [Pt(N₃)_nCl_6–n]^2– and [Pt(¹⁵NN₂)_n(N₂¹⁵N)_6–n]^2–, n = 0–6 By ligand exchange of [PtCl₆]^2– with sodium azide mixed complexes of the series [Pt(N₃)_nCl_6–n]^2– and with ¹⁵N‐labelled sodium azide (Na¹⁵NN₂) mixtures of the isotopomeres [Pt(¹⁵NN₂)_n(N₂¹⁵N)_6–n]^2–, n = 0–6 and the pair [Pt(¹⁵NN₂)Cl₅]^2–/[Pt(N₂¹⁵N)Cl₅]^2– are formed. X‐ray structure determinations on single crystals of (Ph₄P)₂[Pt(N₃)₆] ( 1 ) (triclinic, space group P1, a = 10.175(1), b = 10.516(1), c = 12.380(2) Å, α = 87.822(9), β = 73.822(9), γ = 67.987(8)°, Z = 1) and (Ph₄As)₂[Pt(N₃)Cl₅] · HCON(CH₃)₂ ( 2 ) (triclinic, space group P1, a = 10.068(2), b = 11.001(2), c = 23.658(5) Å, α = 101.196(14), β = 93.977(15), γ = 101.484(13)°, Z = 2) have been performed. The bond lengths are Pt–N = 2.088 ( 1 ), 2.105 ( 2 ) and Pt–Cl = 2.318 Å ( 2 ). The approximate linear azido ligands with N^α–N^β–N^γ‐angles = 173.5–174.6° are bonded with Pt–N^α–N^β‐angles = 116.4–121.0°. In the vibrational spectra the PtCl stretching vibrations of (n‐Bu₄N)₂[Pt(N₃)Cl₅] are observed at 318–345, the PtN stretching modes of (n‐Bu₄N)₂[Pt(N₃)₆] at 401–428 and of (n‐Bu₄N)₂[Pt(N₃)Cl₅] at 408–413 cm^–1. The mixtures (n‐Bu₄N)₂[Pt(¹⁵NN₂)_n(N₂¹⁵N)_6–n], n = 0–6 and (n‐Bu₄N)₂[Pt(¹⁵NN₂)Cl₅]/(n‐Bu₄N)₂[Pt(N₂¹⁵N)Cl₅] exhibit ¹⁵N‐isotopic shifts up to 20 cm^–1. Based on the molecular parameters of the X‐ray determinations the vibrational spectra are assigned by normal coordinate analysis. The average valence force constants are f_d(PtCl) = 1.93, f_d(PtN^α) = 2.38 and f_d(N^αN^β, N^βN^γ) = 12.39 mdyn/Å. In the ¹⁹⁵Pt NMR spectrum of [Pt(N₃)_nCl_6–n]^2–, n = 0–6 downfield shifts with the increasing number of azido ligands are observed in the range 4766–5067 ppm. The ¹⁵N NMR spectrum of (n‐Bu₄N)₂[Pt(¹⁵NN₂)_n(N₂¹⁵N)_6–n], n = 0–6 exhibits by ¹⁵N–¹⁹⁵Pt coupling a pseudotriplett at –307.5 ppm. Due to the isotopomeres n = 0–5 for terminal ¹⁵N six well‐resolved signals with distances of 0.03 ppm are observed in the low field region at –201 to –199 ppm.     

Darstellung,Kristallstruktur, Schwingungsspektren und Normalkoordinatenanalyse von (Ph4P)2[OsN(N3)5] und 15N‐NMR‐Verschiebungen von Nitridoosmaten(VI,VIII)

Synthesis, Crystal Structure, Vibrational Spectra, and Normal Coordinate Analysis of (Ph₄P)₂[OsN(N₃)₅] and ¹⁵N NMR Chemical Shifts of Nitridoosmates(VI, VIII) The treatment of (Ph₄P)[OsNCl₄] with NaN₃ yields (Ph₄P)₂[OsN(N₃)₅], which crystal structure has been determined by single crystal X‐ray diffraction analysis (monoclinic, space group P 2₁/a, a = 20.484(6), b = 11.168(1), c = 20.666(4) Å, β = 97.35(3)°, Z = 4). The IR and Raman vibrations were assigned by a normal coordinate analysis based on the molecular parameters of the X‐ray determination. The valence force constants are f_d(Os≡N) = 8.52, f_d(Os–N^α) = 1.99, f_d(N^α–N^β) = 12.42, f_d(N^β–N^γ) = 12.73 and for the azido ligand in trans‐position to the nitrido group f_d(Os–N^{α ·} ) = 1.84, f_d(N^{α ·} –N^{β ·} ) = 11.91, f_d(N^{β ·} –N^{γ ·} ) = 12.18 mdyn/Å. The ¹⁵N NMR spectra of various nitridoosmates reveal the chemical shifts δ(¹⁵N) for K[OsO₃¹⁵N] = 387.6, K₂[Os¹⁵NCl₅] = 446.7, (Ph₄P)[Os¹⁵NCl₄] = 352.9, [(n‐C₆H₁₃)₄N]₂[Os¹⁵N(N₃)₅] = 307.3 and for [(n‐Pr)₄N]₂[Os¹⁵N(¹⁵NCO)₅] = 483,7 (Os≡N), –417,7 (OsNCO_eq) und –392,8 ppm (OsNCO_ax).     

Darstellung,Kristallstrukturen und Schwingungsspektren von trans‐[Pt(N3)4(ECN)2]2–, E = S,Se

Synthesis, Crystal Structures, and Vibrational Spectra of trans ‐[Pt(N₃)₄(ECN)₂]^2–, E = S, Se By oxidative addition to (n‐Bu₄N)₂[Pt(N₃)₄] with dirhodane in dichloromethane trans‐(n‐Bu₄N)₂[Pt(N₃)₄(SCN)₂] and by ligand exchange of trans(n‐Bu₄N)₂[Pt(N₃)₄I₂] with Pb(SeCN)₂ trans‐(n‐Bu₄N)₂[Pt(N₃)₄(SeCN)₂] are formed. X‐ray structure determinations on single crystals of trans‐(Ph₄P)₂[Pt(N₃)₄(SCN)₂] (triclinic, space group P 1, a = 10.309(3), b = 11.228(2), c = 11.967(2) Å, α = 87.267(13), β = 75.809(16), γ = 65.312(17)°, Z = 1) and trans‐(Ph₄P)₂[Pt(N₃)₄(SeCN)₂] (triclinic, space group P 1, a = 9.1620(10), b = 10.8520(10), c = 12.455(2) Å, α = 90.817(10), β = 102.172(10), γ = 92.994(9)°, Z = 1) reveal, that the compounds crystallize isotypically with octahedral centrosymmetric complex anions. The bond lengths are Pt–S = 2.337, Pt–Se = 2.490 and Pt–N = 2.083 (S), 2.053 Å (Se). The approximate linear Azidoligands with N^α–N^β–N^γ‐angles = 172,1–175,0° are bonded with Pt–N^α–N^β‐angles = 116,7–120,5°. In the vibrational spectra the platinum chalcogen stretching vibrations of trans‐(n‐Bu₄N)₂[Pt(N₃)₄(ECN)₂] are observed at 296 (E = S) and in the range of 186–203 cm^–1 (Se). The platinum azide stretching modes of the complex salts are in the range of 402–425 cm^–1. Based on the molecular parameters of the X‐ray determinations the IR and Raman spectra are assigned by normal coordinate analysis. The valence force constants are f_d(PtS) = 1.64, f_d(PtSe) = 1.36, f_d(PtN^α) = 2.33 (S), 2.40 (Se) and f_d(N^αN^β, N^βN^γ) = 12.43 (S), 12.40 mdyn/Å (Se).     

Darstellung,Kristallstruktur und Schwingungsspektren von cis‐(CH2Py2)[ReBr4Py2]2 · (CH3)2CO

Synthesis, Crystal Structure, and Vibrational Spectra of cis ‐(CH₂Py₂)[ReBr₄Py₂]₂ · (CH₃)₂CO By reaction of (n‐Bu₄N)₂[ReBr₆] with pyridine and (n‐Bu₄N)BH₄ in dichloromethane halogeno‐pyridine‐rhenium(III)complexes are formed and purified by chromatography. X‐ray structure determination on a single crystal has been performed of cis‐(CH₂Py₂)[ReBr₄Py₂]₂ · (CH₃)₂CO (monoclinic, space group P2₁/c, a = 15.0690(9), b = 8.3337(8), c = 35.588(4) Å, β = 96.409(7), Z = 4). Based on the molecular parameters of the X‐ray structure determination and assuming C₂ point symmetry for the anion cis‐[ReBr₄Py₂]^– the IR and Raman spectra are assigned by normal coordinate analysis. The valence force constants are in the Br–Re–Br axis f_d(ReBr) = 1.49, in the asymmetrically coordinated N′–Re–Br ^· axes f_d(ReBr ^· ) = 1.03 und f_d(ReN′) = 2.52 mdyn/Å.     

Synthesen und NMR‐Untersuchungen von Salzen mit den neuen Anionen [PtXn(CF3)6‐n]2— (n = 0 ‐ 5, X = F,OH, Cl,CN) und die Kristallstrukturanalyse von K2[(CF3)2F2Pt(μ‐OH)2PtF2(CF3)2]·2H2O

Syntheses and NMR Spectroscopic Ivestigations of Salts containing the Novel Anions [PtX_n(CF₃)_6‐n]^2— (n = 0 ‐ 5, X = F, OH, Cl, CN) and Crystal Structure of K₂[(CF₃)₂F₂Pt(μ‐OH)₂PtF₂(CF₃)₂]·2H₂O The first syntheses of trifluoromethyl‐complexes of platinum through fluorination of cyanoplatinates are reported. The fluorination of tetracyanoplatinates(II), K₂[Pt(CN)₄], and hexacyanoplatinates(IV), K₂[Pt(CN)₆], with ClF in anhydrous HF leads after working up of the products to K₂[(CF₃)₂F₂Pt(μ‐OH)₂PtF₂(CF₃)₂]·2H₂O. The structure of the salt is determined by a X‐ray structure analysis, P2₁/c (Nr. 14), a = 11.391(2), b = 11.565(2), c = 13.391(3)Å, β = 90.32(3)°, Z = 4, R₁ = 0.0326 (I > 2σ(I)). The reaction of [Bu₄N]₂[Pt(CN)₄] with ClF in CH₂Cl₂ generates mainly cis‐[Bu₄N]₂[PtCl₂(CF₃)₄] and fac‐[Bu₄N]₂[PtCl₃(CF₃)₃], but in contrast that of [Bu₄N]₂[Pt(CN)₆] with ClF in CH₂Cl₂ results cis‐[Bu₄N]₂[PtX₂(CF₃)₄], [Bu₄N]₂[PtX(CF₃)₅] (X = F, Cl) and [Bu₄N]₂[Pt(CF₃)₆]. In the products [Bu₄N]₂[PtX_n(CF₃)_6‐n] (X = F, Cl, n = 0—3) it is possibel to exchange the fluoro‐ligands into chloro‐ and cyano‐ligands by treatment with (CH₃)₃SiCl und (CH₃)₃SiCN at 50 °C. With continuing warming the trifluoromethyl‐ligands are exchanged by chloro‐ and cyano‐ligands, while as intermediates CF₂Cl and CF₂CN ligands are formed. The identity of the new trifluoromethyl‐platinates is proved by ¹⁹⁵Pt‐ and ¹⁹F‐NMR‐spectroscopy.     

Darstellung und Eigenschaften von trans-Di(fluoro)phthalocyaninato(2–)-rhenat(III); Kristallstruktur des linear-Bis(triphenylphosphin)iminium-Doppelsalzes l(PNP)trans[Re(F)2pc2–] · 0,33l(PNP)F · 2 H2O

Synthesis and Properties of trans -Di(fluoro)phthalocyaninatorhenate(III); Crystal Structure of the linear -Bis(triphenylphosphine)iminium Double Salt ^l (PNP) ^trans[Re(F)₂pc^2–] · 0.33^l (PNP)F · 2 H₂O trans-Bis(triphenylphosphine)phthalocyaninato(2–)rhenium(II) reacts with (ⁿBu₄N)F · 3 H₂O in acetone on air yielding trans-di(fluoro)phthalocyaninato(2–)rhenate(III), ^trans[Re(F)₂pc^2–]^–. The complex anion is precipitated as tetra(n-butyl)ammonium (ⁿBu₄N), or after addition of (PNP)HSO₄ as linear-bis(triphenylphosphine)iminium (^l(PNP)) salt. The latter crystallizes as a double salt of formula ^l(PNP)^trans[Re(F)₂pc^2–] · 0.33^l(PNP)F · 2 H₂O in the cubic space group I23 (no. 197) with the cell parameter a = 21.836(2) Å; V = 10412(2) ų; Z = 6. The Re atom is located in the centre of the (N_iso)₄ plane (N_iso: isoindole-N atom) and coordinates axially two fluorine atoms in a mutual trans position. The Re–N and Re–F distance is 2.035(6) and 1.798(7) Å, respectively. According to the short Re–F distance the asymmetric Re–F stretching vibration is observed in the MIR spectrum at 746 cm^–1. Obviously due to a large spin-orbit coupling, the complex salt with an electronic low-spin d⁴ ground state of Re^III (S = 1) is diamagnetic. Hence a sharp signal is observed at –126.1 ppm in the ¹⁹F NMR spectrum. The UV-VIS-NIR spectrum shows the typical π-π* transitions at 15000 (B), 29500 (Q) and 36900 cm^–1 (N) and trip-multiplet transitions at 9500/10500 cm^–1 and 13200/14100 cm^–1.     

A rare octacoordinated mononuclear iron(III) spin‐crossover compound: synthesis,crystal structure and magnetic properties

The chemistry of transition‐metal complexes with unusually high coordination numbers has been of interest because of their application in catalytic and biological systems. Deprotonation of the ionogenic tetradentate ligand 6,6′‐bis(1H‐tetrazol‐5‐yl)‐2,2′‐bipyridine [H₂bipy(ttr)₂] in the presence of iron(III) and tetra‐n‐butylammonium bromide, [n‐Bu₄N]Br, in solution resulted in the synthesis of a rare octacoordinated anionic mononuclear complex, tetra‐n‐butylammonium bis[6,6′‐bis(tetrazol‐1‐id‐5‐yl)‐2,2′‐bipyridine]iron(III) methanol hemisolvate dihydrate, (C₁₆H₃₆N)[Fe(C₁₂H₆N₁₀)₂]·0.5CH₃OH·2H₂O or [n‐Bu₄N][Fe{bipy(ttr)₂}₂]·0.5CH₃OH·2H₂O ( 1 ), which has been structurally characterized by elemental analysis, powder X‐ray diffraction (PXRD) and single‐crystal X‐ray diffraction. In 1 , the coordination sphere of the iron(III) ion is a distorted bis‐disphenoid dodecahedron, in which the eight coordination positions are occupied by eight N atoms from two independent tetradentate [bipy(ttr)₂]^2? anionic ligands, therefore forming the anionic [Fe{bipy(ttr)₂}₂]^? unit, with the negative charge balanced by a free [n‐Bu₄N]⁺ cation. An investigation of the magnetic properties of 1 revealed a gradual incomplete spin‐crossover behaviour below 150 K.     

Darstellung und Eigenschaften von Diphthalocyaninaten des Bismuts, [Bi(Pc)2]k (k = 1−, 0, 1+); Kristallstruktur von gemischtvalentem [Bi(Pc)2] · CH2Cl2

Synthesis and Properties of Diphthalocyaninates of Bismuth, [Bi(Pc)₂]^k (k = 1?, 0, 1+); Crystal Structure of mixed-valent [Bi(Pc)₂] · CH₂Cl₂ Blue di(phthalocyaninato(2-))bismuthate(III), [Bi(Pc^2?)₂]^?, is obtained by the reaction of BiO(NO₃) with molten 1,2-dicyanobenzene in the presence of potassium methylate and isolated as tetra-n-butylammonium (ⁿBu₄N)⁺ and bis(triphenylphosphine)iminium (PNP)⁺ salt. Green mixed-valent [Bi(Pc)₂] · CH₂Cl₂ is prepared by anodic oxidation of [Bi(Pc^2?)₂]^?. It crystallizes in the orthorhombic γ modification (Pnma; a = 28.176(5), b = 22.913(3), c = 7.925(1) Å, Z = 4). The Bi^III ion is eightfold coordinated by the N_iso atoms of the slightly distorted Pc ligands in a square antiprismatic manner. The average Bi? N_iso bond distance is 2.467 Å. The complex is paramagnetic (μ_eff = 1.84 μ_B). Oxidation of [Bi(Pc^2?)₂]^? with bromine yields purple, diamagnetic [Bi(Pc^?)₂]Br_x (1.5 ≤ x ≤ 2.5). The redox properties are investigated electrochemically. UV-Vis-NIR, MIR/FIR and resonance Raman spectra of the new bismuth(III) complexes are discussed and compared with those of diphthalocyaninates of the lanthanides.     

Kristallstrukturen,Schwingungsspektren und Normalkoordinatenanalyse von (n‐Bu4N)2[Os(NCS)6] und (n‐Bu4N)3[Os(NCS)6]

Crystal Structure, Vibrational Spectra, and Normal Coordinate Analysis of ( n ‐Bu₄N)₂[Os(NCS)₆] and ( n ‐Bu₄N)₃[Os(NCS)₆] By tempering the solid mixture of the linkage isomers (n‐Bu₄N)₃[Os(NCS)_n(SCN)_6–n] n = 0–5 for a longer time at temperatures increasing from 60 to 140 °C the homoleptic (n‐Bu₄N)₃[Os(NCS)₆] is formed, which on oxidation with (NH₄)₂[Ce(NO₃)₆] in acetone yields the corresponding Os^IV complex (n‐Bu₄N)₂[Os(NCS)₆]. X‐ray structure determinations on single crystals of (n‐Bu₄N)₂[Os(NCS)₆] (1) (triclinic, space group P 1, a = 12.596(5), b = 12.666(5), c = 16.026(5) Å, α = 88.063(5), β = 80.439(5), γ = 88.637(5)°, Z = 2) and (n‐Bu₄N)₃[Os(NCS)₆] ( 2 ) (cubic, space group Pa 3, a = 24.349(4) Å, Z = 8) have been performed. The nearly linear thiocyanate groups are coordinated with Os–N–C angles of 172.3–177.7°. Based on the molecular parameters of the X‐ray determinations the IR and Raman spectra are assigned by normal coordinate analysis. The valence force constant f_d(OsN) is 2.3 ( 1 ) and 2.10 mdyn/Å ( 2 ).     

(n‐Bu4N)2[Au(mnt)2]: Synthese,Struktur‐ und EPR‐Untersuchungen eines stabilen,mononuklearen AuII‐Komplexes

The reaction of [Au^III(mnt)₂]^? with (n‐Bu₄N)[BH₄] in acetone leads to the formation of [Au^II(mnt)₂]^2?, which is the second stable mononuclear Au^II complex characterized by X‐ray structure analysis. (n‐Bu₄N)₂[Au^II(mnt)₂] crystallizes triclinic, P (a = 904.24(5), b = 989.55(5), c = 1627.35(10) pm, α = 92.040(7), β = 94.937(7), γ = 107.220(6)°, Z = 1) with two molecules acetone per unit cell. The anion is planar. From EPR investigations using single crystals of (n‐Bu₄N)₂[Au^II(mnt)₂] the g tensor components were derived. Information about magnetic exchange interactions were obtained from line width analyses.     

Synthese und Kristallstrukturen von (Ph4P)4[Bi8I28], (nBu4N)[Bi2I7] und (Et3PhN)2[Bi3I11] – Iodobismutate mit isolierten bzw. polymeren Anionen

Synthesis and Crystal Structures of (Ph₄P)₄[Bi₈I₂₈], (ⁿBu₄N)[Bi₂I₇], and (Et₃PhN)₂[Bi₃I₁₁] – Bismuth Iodo Complexes with Isolated and Polymeric Anions Solutions of BiI₃ in methanol react with NaI and (ⁿBu₄N)(PF₆) or (Et₃NPh)(PF₆) to form anionic bismuth iodo complexes (ⁿBu₄N)[Bi₂I₇] 1 and (Et₃PhN)₂[Bi₃I₁₁] 2 . In 1 Bi₄I₁₆ units, and in 2 Bi₆I₂₄ units are linked by common I-atoms to onedimensional infinite chains. Reaction of BiI₃ with (Ph₄P)(PF₆) in methanol yields (Ph₄P)₄[Bi₈I₂₈] 3 . The anions of 1–3 consist of edge-sharing BiI₆ octahedra. (ⁿBu₄N)[Bi₂I₇] 1 : Space group I2/m (No. 13), a = 1 082.3(5), b = 2 597.1(13), c = 1 206.1(6) pm, β = 93.17(2)°, V = 3 385(3) · 10⁶ pm³; (Et₃PhN)₂[Bi₃I₁₁] 2 : Space group P1 (No. 2), a = 1 283.5(6), b = 1 345.9(7), c = 1 546.3(8) pm, α = 83.87(2), β = 74.24(2), γ = 68.26(2)°, V = 2 388(2) · 10⁶ pm³; (Ph₄P)₄[Bi₈I₂₈] 3 : Space group P1 (No. 2), a = 1 329.3(4), b = 1 337.0(4), c = 2 193.1(5) pm, α = 104.20(2), β = 99.73(2), γ = 100.44(2)°, V = 3 622(2) · 10⁶ pm³.     

Darstellung,Kristallstrukturen und Schwingungsspektren von trans‐[Pt(N3)4X2]2–, X = Cl,Br, I

Synthesis, Crystal Structures, and Vibrational Spectra of trans ‐[Pt(N₃)₄X₂]^2–, X = Cl, Br, I By oxidative addition to (n‐Bu₄N)₂[Pt(N₃)₄] with the elemental halogens in dichloromethane trans‐(n‐Bu₄N)₂[Pt(N₃)₄X₂], X = Cl, Br, I are formed. X‐ray structure determinations on single crystals of trans‐(Ph₄P)₂[Pt(N₃)₄Cl₂] (triclinic, space group P1, a = 10.352(1), b = 10.438(2), c = 11.890(2) Å, α = 91.808(12), β = 100.676(12), γ = 113.980(10)°, Z = 1), trans‐(Ph₄P)₂[Pt(N₃)₄Br₂] (triclinic, space group P1, a = 10.336(1), b = 10.536(1), c = 12.119(2) Å, α = 91.762(12), β = 101.135(12), γ = 112.867(10)°, Z = 1) and trans‐(Ph₄P)₂[Pt(N₃)₄I₂] (triclinic, space group P1, a = 10.186(2), b = 10.506(2), c = 12.219(2) Å, α = 91.847(16), β = 101.385(14), γ = 111.965(18)°, Z = 1) reveal, that the compounds crystallize isotypically with octahedral centrosymmetric complex anions. The bond lengths are Pt–Cl = 2.324, Pt–Br = 2.472, Pt–I = 2.619 and Pt–N = 2.052–2.122 Å. The approximate linear Azidoligands with N^α–N^β–N^γ‐angles = 172.1–176.8° are bonded with Pt–N^α–N^β‐angles = 116.2–121.9°. In the vibrational spectra the platinum halogen stretching vibrations of trans‐(n‐Bu₄N)₂[Pt(N₃)₄X₂] are observed in the range of 327–337 (X = Cl), at 202 (Br) and in the range of 145–165 cm^–1 (I), respectively. The platinum azide stretching modes of the three complex salts are in the range of 401–421 cm^–1. Based on the molecular parameters of the X‐ray determinations the IR and Raman spectra are assigned by normal coordinate analysis. The valence force constants are f_d(PtCl) = 1.90, f_d(PtBr) = 1.64, f_d(PtI) = 1.22, f_d(PtN^α) = 2.20–2.27 and f_d(N^αN^β, N^βN^γ) = 12.44 mdyn/Å.