2‐Chloro‐1, 3‐diisopropyl‐4, 5‐dimethylimidazolium Dichlorophosphate. First Structural Characterisation of the [PO2Cl2]— Anion [1]

The X‐ray structure of 2‐Chloro‐1, 3‐diisopropyl‐4, 5‐dimethylimidazolium dichlorophosphate ( 2 ) (obtained from 2‐chloro‐1, 3‐diisopropyl‐4, 5‐dimethylimidazolium chloride 1 and POCl₃ in the presence of water) is reported.     

Synthesis and Structure of a One‐Dimensional Aluminum Phosphate, [NH3(CH2)2NH2(CH2)3NH3]3+ [Al(PO4)2]3—

A one‐dimensional aluminum phosphate, [NH₃(CH₂)₂NH₂(CH₂)₃NH₃]³⁺ [Al(PO₄)₂]^3—, has been synthesized hydrothermally in the presence of N‐(2‐Aminoethyl‐)1, 3‐diaminopropane (AEDAP) and its structure determined by single crystal X‐ray diffraction. Crystal data: space group = Pbca (no. 61), a = 16.850(2), b = 8.832(1), c = 17.688(4)Å, V = 2632.4(2)ų, Z = 8, R₁ = 0.0389 [5663 observed reflections with I > 2σ(I)]. The structure consists of anionic [Al(PO₄)₂]^3— chains built up from AlO₄ and PO₄ tetrahedra, in which all the AlO₄ vertices are shared and each PO₄ tetrahedron possesses two terminal P=O linkages. The cations, which balances the negative charge of the chains, are located in between the chains and interact with the oxygen atoms through strong N—H···O hydrogen bonds. Additional characterization of the compound by powder XRD and MAS‐NMR has also been performed and described.     

In Pursuit of the PO2+ Cation. The Reaction of KPO2F2 and SbF5 leads to an Eight‐membered Antimony‐Oxygen‐Phosphorus‐bridged Ring

The reaction of KPO₂F₂ with the strong Lewis acid SbF₅ was studied as a potential pathway to the unknown PO₂⁺ cation. The resulting product has the desired PO₂SbF₆ composition but consists of an eight‐membered, antimony‐oxygen‐phosphorus‐bridged ring that was characterized by vibrational and NMR spectroscopy, ab initio methods, and a single crystal x‐ray diffraction study. The preferred formation of the ring and its mechanism are discussed.     

1‐Phosphabicyclo[2.2.1]heptane

1‐Phosphabicyclo[2.2.1]heptanes Exo‐endo‐ and exo‐exo‐2.6‐dimethyl‐1‐phosphabicyclo [2.2.1]heptane have been obtained by cyclization of 2‐methyl‐4‐(2‐propenyl)phospholane in the presence of the complex base, sodium salt of diethylenglycolmonoethylether ‐ sodium amide in THF (NAMEDEG). The bicyclic phosphanes are characterized by reac‐tions with selenium, sulfur, (CH₃)₂SeO, CH₃I and HSO₃F, respectively, elemental analysis, X‐ray crystal structure analysis as well as ¹H, ¹³C, ³¹P NMR spectral measurements. The steric demand of these phosphanes as complex ligands has been estimated from the P, H coupling constants of the phosphonium fluorosulphates according to the Tolman model. The phosphane selenides were found to display the lowest values for the ¹J(Se, P) coupling constant, found up to now for alicyclic and cyclic aliphatic tertiary phosphane selenides. The ⁿJ(P, H)‐ and ⁿJ(H, H)_{n=2, 3} coupling constants have been extracted from the proton spectra at 600 MHz by computerized analysis.     

Bildung und Struktur von [μ‐(1,2 : 2‐η‐tBu2P–P){Mo(CO)2cp′}2]

Coordination Chemistry of P‐rich Phosphanes and Silylphosphanes. XXIV. Formation and Structure of [μ‐(1,2 : 2‐η‐^tBu₂P–P){Mo(CO)₂cp′}₂] [cp′Mo(CO)₂]₂ (cp′ = C₅H₄^tBu) reacts with ^tBu₂P–P=P(Me)^tBu₂ to yield the compound [μ‐(1,2 : 2‐η‐^tBu₂P–P){Mo(CO)₂cp′}₂], which crystallizes in the space group P2₁2₁2₁ with a = 1202.42(7), b = 1552.48(8), and c = 1765.3(1) pm.     

Molecular and Supramolecular Structures of 1‐Phenyl‐4‐phenylacetyl‐2‐thiosemicarbazide (H2L) and its Complexes with Diphenyllead(IV) Chloride and Acetate

Reaction of 1‐phenyl‐4‐phenylacetyl‐2‐thiosemicarbazide (H₂L) with diphenyllead(IV) dichloride and acetate afforded the complexes [PbPh₂Cl₂(H₂L)₂] and [PbPh₂L]. The ligand and the complexes were characterized by elemental analyses, ¹H and ¹³C NMR spectroscopy and X‐ray crystallography. In the asymmetric unit of crystals of the ligand there are four independent molecules of H₂L and four molecules of water, which associate in the lattice as two independent sheets. The complex [PbPh₂Cl₂(H₂L)₂]·4MeOH has slightly distorted all‐trans octahedral geometry around the lead atom, and the fact that the ligand is S‐bound rather than O‐bound suggests that PbPh₂Cl₂ behaves as a “soft” Lewis acid. Hydrogen bonds involving NH groups, Cl atoms and MeOH molecules form a three‐dimensional supramolecular structure. In [PbPh₂L]·Me₂CO, the L^2? anion bridges between two metal centres, binding to one strongly via the N and S atoms and weakly via the O atom, and to the other via the O atom, thus creating polymeric chains along the b axis. The double deprotonation and metallation of H₂L induce significant changes in its configuration and lengthen the C‐S and C‐O bonds, suggesting an evolution of the dianion towards a thiol‐enol form.     

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.     

Kristallstrukturen,Normalkoordinatenanalysen und 15N‐NMRund 77Se‐NMR‐Verschiebungen von trans‐[OsO2(NCO)4]2–, trans‐[OsO2(NCS)4]2– und trans‐[OsO2(SeCN)4]2–

Crystal Structures, Normal Coordinate Analyses, and ¹⁵N NMR and ⁷⁷Se NMR Chemical Shifts of trans ‐[OsO₂(NCO)₄]^2–, trans ‐[OsO₂(NCS)₄]^2–, and trans ‐[OsO₂(SeCN)₄]^2– The crystal structures of trans‐(Ph₃PNPPh₃)₂[OsO₂(NCO)₄] ( 1 ) (orthorhombic, space group Pbca, a = 19.278(3), b = 16.674(4), c = 19.982(2) Å, Z = 4), trans(n‐Bu₄N)₂[OsO₂(NCS)₄] ( 2 ) (triclinic, space group P1, a = 12.728(3), b = 12.953(3), c = 16.255(6) Å, α = 97.39(4), β = 105.62(2), γ = 95.25(3)°, Z = 2) and trans‐(n‐Bu₄N)₂[OsO₂(SeCN)₄] ( 3 ) (tetragonal, space group I4/m, a = 13.406(2), c = 12.871(1) Å, Z = 2) have been determined by single‐crystal X‐ray diffraction analysis, showing the bonding of NCO and NCS via the N atom but the coordination of SeCN via the Se atom to osmium. Based on the molecular parameters of the X‐ray determinations the vibrational spectra have been assigned by normal coordinate analyses. The valence force constants are for 1 f_d(OsO) = 6.43, f_d(OsN) = 3.32, f_d(NC) = 14.50, f_d(CO) = 12.80, for 2 f_d(OsO) = 6.56, f_d(OsN) = 1.75, f_d(NC) = 15.00, f_d(CS) = 5.50, and for 3 f_d(OsO) = 6.75, f_d(OsSe) = 0.99, f_d(SeC) = 3.23, f_d(CN) = 15.95 mdyn/Å. The observed NMR shifts are δ(¹⁵N) = –386.6 ( 1 ), δ(¹⁵N) = –294.7 ( 2 ) and δ(⁷⁷Se) = 108.8 ppm ( 3 ).     

Synthesis of Ammonium‐ and 4‐Dimethylaminopyridinium Amidofluorophosphates and Crystal Structure of [DMAPH][PO2F(NH2)]

NH₄[PO₂F(NH₂)] has been prepared by the reaction of a betaine py·PO₂F with excess ammonia in acetonitrile solution, while the ammonolysis of DMAP·PO₂F with a stoichiometric amount of NH₃ yields [DMAPH][PO₂F(NH₂)]. The crystal structure of the latter was determined by single‐crystal X‐ray diffraction, which revealed that the anions [PO₂F(NH₂)]^— are linked to infinite chains by double N—H···O bridges. Additional strong N—H···O bridging bonds connect each anion with its [DMAPH]⁺ counterion. The formation of a new betaine NH₃·PO₂F in the solution of py·PO₂F in liquid ammonia was proved by ³¹P NMR spectroscopy and by identification of its hydrolysis products.     

Synthesis,Characterization, and Crystal Structure of 1,3‐Dipentafluorophenyl‐2,2,2,4,4,4‐hexazido‐1,3‐diaza‐2,4‐diphosphetidine

1,3‐Dipentafluorophenyl‐2,2,2,4,4,4‐hexazido‐1,3‐diaza‐2,4‐diphosphetidine ( 1 ) was synthesized by the reaction of [(C₆F₅)NPCl₃]₂ with trimethylsilyl azide in CH₂Cl₂ and characterized by multinuclear NMR and vibrational spectroscopy. The molecular structure of the compound was determined by single‐crystal X‐ray structure analysis. [(C₆F₅)NP(N₃)₃]₂ crystallizes in the monoclinic space group P2₁/n with a = 9.6414(2), b = 7.4170(1) and c = 15.9447(4) Å, β = 94.4374(9)°, with 2 formula units per unit cell. The bond situation in [(C₆F₅)NP(N₃)₃]₂ has been studied on the basis of NBO analysis. The antisymmetric stretching vibration of the azide groups is discussed. The structural diversity of 1 and 1,3‐diphenyl‐2,2,2,4,4,4‐hexazido‐1,3‐diaza‐2,4‐diphosphetidine in solution and in the solid state depending on the aryl substituent at the nitrogen atom is discussed.     

Multianvil‐Synthese,Pulver‐Röntgenstrukturanalyse, 31P‐MAS‐NMR‐ und FTIR‐Spektroskopie sowie Materialeigenschaften von γ‐P3N5, einer Hochdruckphase von binärem Phosphor(V)‐nitrid mit verzerrt quadratischen PN5‐Pyramiden und PN4‐Tetraedern

Multianvil Synthesis, X‐ray Powder Diffraction Analysis, ³¹P‐MAS‐NMR, and FTIR Spektroscopy as well as Material Properties of γ‐P₃N₅, a High‐Pressure Polymorph of Binary Phosphorus(V) Nitride, Built up from Distorted PN₅ Square Pyramids and PN₄ Tetrahedra The high‐pressure phase γ‐P₃N₅ was synthesized at a pressure of 11 GPa and a temperature of 1500 °C in a multianvil apparatus. Partially crystalline P₃N₅ has been used as a starting material. The crystal structure was solved by direct methods on the basis of X‐ray powder diffraction data and it was refined by the Rietveld method (Imm2, a = 1287.21(4), b = 261.312(6), c = 440.03(2) pm, Z = 2, R_p = 0.073, wR_p = 0.094, R_F = 0.048). γ‐phosphorus nitride crystallizes in a three‐dimensional network structure built up from corner sharing PN₄ tetrahedra and trans‐edge sharing distorted PN₅ square pyramids. In the ³¹P‐MAS‐NMR spectrum two sharp isotropic resonances with an intensity ratio of 1 : 2.02(5) are observed at —11.95(3) and —101.72(7) ppm, respectively. The IR‐spectroscopic and thermal properties of γ‐P₃N₅ are described. Measurement of the Vickers hardness resulted in a value of 9.7(21) GPa for sintered polycrystalline γ‐P₃N₅, which is significantly higher than that for the partially crystalline normal pressure modification of P₃N₅ (5.1(7) GPa).     

Reaktionen von tBu2P–P=P(Me)tBu2 mit (Et3P)2NiCl2 und [{η2‐C2H4}Ni(PEt3)2]

Coordination Chemistry of P‐rich Phosphanes and Silylphosphanes. XXIII. Reactions of ^tBu₂P–P=P(Me)^tBu₂ with (Et₃P)₂NiCl₂ and [{η²‐C₂H₄}Ni(PEt₃)₂] ^tBu₂P–P=P(Me)^tBu₂ ( 1 ) forms with (Et₃P)₂NiCl₂ ( 2 ) and Na(Nph) the [μ‐(1,3 : 2,3‐η‐^tBu₂P₄^tBu₂){Ni(PEt₃)Cl}₂] ( 3 ) as main product. Using Na/Hg instead as reducing agent the Ni⁰ compounds [{η²‐^tBu₂P–P}Ni(PEt₃)₂] ( 4 ), [{η²‐^tBu₂P–P=P–P^tBu₂}Ni(PEt₃)₂] ( 5 ) and [(Et₃P)Ni(μ‐P^tBu₂)]₂ ( 6 ) with four‐membered Ni₂P₂ ring result. [{η²‐C₂H₄}Ni(PEt₃)₂] yields with 1 also 4 . The compounds were characterized by ¹H and ³¹P{¹H} NMR investigations and 3 also by a single crystal X‐ray analysis. It crystallizes triclinic in the space group P 1 with a = 1129.4(2), b = 1256.8(3), c = 1569.5(3) pm, α = 72.44(3)°, β = 70.52(3)° and γ = 74.20(3)°.     

Darstellung,Kristallstrukturen, Schwingungsspektren und Normalkoordinatenanalyse von [PtX2ox]2−, X = Cl,Br

Synthesis, Crystal Structure, Vibrational Spectra, and Normal Coordinate Analysis of [PtX₂ox]²⁻, X = Cl, Br By treatment of [PtX₄]^2— (X = Cl, Br) with C₂O₄^2— (ox^2—) in water [PtCl₂ox]^2— and [PtBr₂ox]^2— are formed which have been isolated by ion exchange chromatography on diethylaminoethyl cellulose. The crystal structures of [(C₅H₅N)₂CH₂][PtCl₂ox]·2H₂O ( 1 ) (orthorhombic, space group Pbca, a = 18.451(1), b = 18.256(1), c = 19.913(1)Å, Z = 16) and [(C₅H₅N)₂CH₂][PtBr₂ox] ( 2 ) (monoclinic, space group P2₁/c, a = 7.249(1), b = 10.180(1), c = 21.376(1)Å, β = 93.415(9)°, Z = 4) reveal nearly planar complex anions with C_2v point symmetry. The bond lengths are Pt‐Cl = 2.286, Pt‐Br = 2.405 und Pt‐O = 2.016 ( 1 ) und 2.030Å ( 2 ). In the vibrational spectra the PtX stretching vibrations are observed at 335 and 336 ( 1 ) and 219 and 231 cm^—1 ( 2 ). The PtO stretching vibrations are coupled with internal modes of the oxalato ligands and appear in the range of 350 — 800 cm^—1. Using the molecular parameters of the X‐Ray determinations the IR and Raman spectra of the (n‐Bu₄N) salts are assigned by normal coordinate analysis. The valence force constants are f_d(PtCl) = 1.97, f_d(PtBr) = 1.78 and f_d(PtO) = 2.48 ( 1 ) and 2.38 mdyn/Å ( 2 ). Taking into account increments of the trans influence a good agreement between observed and calculated frequencies is achieved. The NMR shifts are δ(¹⁹⁵Pt) = 3603.9 ( 1 ) and 3318.1 ppm ( 2 ).     

Darstellung,Kristallstrukturen, Schwingungsspektren und Normalkoordinatenanalyse von cis‐ und trans‐(n‐Bu4N)2[PtF2(ox)2] und (n‐Bu4N)2[PtF4(ox)]

Synthesis, Crystal Structure, Vibrational Spectra, and Normal Coordinate Analysis of cis‐ and trans‐(n‐Bu₄N)₂[PtF₂(ox)₂] and (n‐Bu₄N)₂[PtF₄(ox)] By treatment of trans‐(n‐Bu₄N)₂[PtCl₂(ox)₂] and (n‐Bu₄N)₂[PtCl₄(ox)] with XeF₂ in propylene carbonate cis‐ and trans‐(n‐Bu₄N)₂[PtF₂(ox)₂] ( 1 , 2 ) and (n‐Bu₄N)₂[PtF₄(ox)] ( 3 ) are formed which have been isolated by ion exchange chromatography on diethylaminoethyl cellulose. The crystal structure of trans(n‐Bu₄N)₂[PtF₂(ox)₂] ( 2 ) (tetragonal, space group P4₂/n, a = 15.5489(9), b = 15.5489(9), c = 17.835(1)Å, Z = 4) und Cs₂[PtF₄(ox)] ( 3 ) (monoclinic, space group C2/m, a = 14.5261(7), b = 6.2719(4), c = 9.6966(9)Å, β = 90.216(8)°, Z = 4) reveal complex anions with nearly D_2h and C_2v point symmetry. The average bond lengths in the symmetrical coordinated axes are Pt—F = 1.93 ( 2 , 3 ) and Pt—O = 1.987 ( 2 ) and in the F^•—Pt—O′‐axes Pt—F^• = 1.957 and Pt—O′ = 1.977Å ( 3 ). The oxalato ligands are nearly planar with a maximum displacement of the ring atoms of 0.05 ( 2 ) und 0.01Å ( 3 ) to the calculated best planes. In the vibrational spectra the symmetric and antisymmetric PtF stretching vibrations are observed at 583 and 586 ( 2 ) and 576 and 568 cm^—1 ( 3 ). The PtF^• modes appear at 565 and 562 ( 1 ) and 560 cm^—1 ( 3 ). The PtO and PtO′ stretching vibrations are coupled with internal modes of the oxalato ligands and appear in the range of 400—800 cm^—1. Based on the molecular parameters of the X‐ray determinations ( 2 , 3 ) and estimated data ( 1 ) the IR and Raman spectra are assigned by normal coordinate analysis. The valence force constants are f_d(PtF) = 3.55 ( 2 ) and 3.38 ( 3 ), f_d(PtF^•) = 3.23 ( 1 ) and 3.20 ( 3 ), f_d(PtO) = 2.65 ( 1 ) and 2.84 ( 2 ) and f_d(PtO′) = 2.97 ( 1 ) and 3.00 mdyn/Å ( 3 ). Taking into account increments of the trans influence a good agreement between observed and calculated frequencies is achieved. The NMR shifts are δ(¹⁹⁵Pt) = 8485 ( 1 ), 8597 ( 2 ) and 10048 ppm ( 3 ), δ(¹⁹F) = —350 ( 2 ) and —352 ( 3 ) and δ(¹⁹F^•) = —323 ( 1 ) and —326 ppm ( 3 ) with the coupling constants ¹J(PtF) = 1784 ( 2 ) and 1864 ( 3 ) and ¹J(PtF^•) = 1525 ( 1 ) and 1638 Hz ( 3 ).     

(Carb)2SnF4 (Carb = 2, 3‐Dihydro‐1, 3‐diisopropyl‐4, 5‐dimethylimidazol‐2‐yliden – ein Carbenkomplex des vierwertigen Zinns

2, 3‐Dihydro‐1, 3‐diisopropyl‐4, 5‐dimethylimidazol‐2‐ylidene ( 1 , Carb) reacts with tin tetrafluoride to give the complex (Carb)₂SnF₄ ( 3 ). The ligand properties of 1 are discussed in terms of the crystal structure and NMR data of 3 .     

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 .     

Neue Halogenochalkogen(IV)‐Säuren: [H3O(Benzo‐18‐Krone‐6)]2[Te2Br10] und [H5O2(Dibenzo‐24‐Krone‐8)]2[Te2Br10]

Novel Halogenochalcogeno(IV) Acids: [H₃O(Benzo‐18‐Crown‐6)]₂[Te₂Br₁₀] and [H₅O₂(Dibenzo‐24‐Crown‐8)]₂[Te₂Br₁₀] Systematic studies on halogenochalcogeno(IV) acids containing tellurium and bromine led to the new crystalline phases [H₃O(Benzo‐18‐Crown‐6)]₂[Te₂Br₁₀] ( 1 ) and [H₅O₂(Dibenzo‐24‐Crown‐8)]₂[Te₂Br₁₀] ( 2 ). The [Te₂Br₁₀]^2‐ anions consists of two edge‐sharing distorted TeBr₆ octahedra, the oxonium cations are stabilized by crownether. ( 1 ) crystallizes in the monoclinic space group P2₁/n with a = 14.520(5) Å, b = 22.259(6) Å, c = 16.053(5) Å, β = 97.76(3)° and Z = 4, whereas ( 2 ) crystallizes in the triclinic space group with a = 11.005(4) Å, b = 12.103(5) Å, c = 14.951(6) Å, α = 71.61(3)°, β = 69.17(3)°, γ = 68.40(3)° and Z = 1.     

Synthesis and Crystal Structure of [Pb(trz)(tfpb)(H2O)]: a Lead(II) Complex Containing 2,4,6‐Tris(2‐pyridyl)‐1,3,5‐triazine and 4,4,4‐Trifluoro‐1‐phenyl‐1,3‐butandionate

[Pb(trz)(tfpb)(H₂O)] ( 1 ) (trz and tfpb are the abbreviations of 2,4,6‐tris(2‐pyridyl)‐1,3,5‐triazine and 4,4,4‐trifluoro‐1‐phenyl‐1,3‐butandionate, respectively) have been synthesized and characterized by elemental analysis and IR, ¹H NMR, spectroscopy. The single‐crystal structure of 1 shows the coordination number of the Pb²⁺ ions is eight with three N‐donor atoms from a “trz” ligand and four O‐donors from the dionate ligand and one molecule of water. The supramolecular features in this complex are guided by lone pair activity and control of strong hydrogen bonds, weak directional intermolecular interactions and aromatic π‐π stacking interactions.     

Darstellung,Kristallstrukturen, Schwingungsspektren und Normalkoordinatenanalyse von trans‐(n‐Bu4N)2[Pt(ECN)2(ox)2], E = S,Se

Synthesis, Crystal Structure, Vibrational Spectra, and Normal Coordinate Analysis of trans ‐( n ‐Bu₄N)₄[Pt(ECN)₂(ox)₂], E = S, Se By reaction of (n‐Bu₄N)₂[Pt(ox)₂] with (SCN)₂ and (SeCN)₂ in dichloromethane trans‐(n‐Bu₄N)₂[Pt(SCN)₂(ox)₂] ( 1 ) und trans‐(n‐Bu₄N)₂[Pt(SeCN)₂(ox)₂] ( 2 ) are formed. The crystal structures of 1 (triclinic, space group P1, a = 10.219(2), b = 11.329(2), c = 12.010(3) Å, α = 114.108(15), β = 104.797(20), γ = 102.232(20)°, Z = 1) and 2 (triclinic, space group P1, a = 10.288(1), b = 11.332(1), c = 12.048(1) Å, α = 114.391(9), β = 103.071(10), γ = 102.466(12)°, Z = 1) reveal, that the compounds crystallize isotypically with centrosymmetric complex anions. The bond lengths are Pt–S = 2.357, Pt–Se = 2.480 and Pt–O = 2.011 ( 1 ) und 2.006 Å ( 2 ). The oxalato ligands are nearly plane with O–C–C–O torsion angles of 1.7–3.6°. The via S or Se coordinated linear groups are inclined between both oxalato ligands with Pt–E–C angles of 100.4 (E = S) and 97.4° (Se). In the vibrational spectra the PtE stretching vibrations are observed at 299–314 ( 1 ) and 189–200 cm^–1 ( 2 ). The PtO stretching vibrations are coupled with internal vibrations of the oxalato ligands and appear in the range of 400–800 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) = 1.75, f_d(PtSe) = 1.35 and f_d(PtO) = 2.77 mdyn/Å. The NMR shifts are δ(¹⁹⁵Pt) = 5435.2 ( 1 ), 5373.7 ( 2 ) and δ(⁷⁷Se) = 353.2 ppm with the coupling constant ¹J(SePt) = 37.4 Hz.