Beiträge zur Chemie des Phosphors. 200. Tetraisopropyl-tetradecaphosphan(4), P14(i-Pr)4 – Darstellung und strukturelle Charakterisierung

Contributions to the Chemistry of Phosphorus. 200. Tetraisopropyl-tetradecaphosphane(4), P₁₄(i-Pr)₄ – Preparation and Structural Characterization Tetraisopropyl-tetradecaphosphane(4) ( 1 ) has been obtained by reacting i-PrPCl₂, P₄, and magnesium and subsequently thermolysing the crude reaction product, and has been isolated in pure form. Whereas the ³¹P{¹H}-NMR spectrum provides only limited structural information, the ¹³C{¹H, ³¹P}-DEPT-NMR and the ¹H{³¹P}-NMR spectrum of 1 reveals the presence of two symmetrical configurational isomers 1a and 1c and one asymmetrical diastereomer 1b . This would only be possible, if 1 is 3,4,10,11-tetraisopropyl-hexacyclo[6.6.0.0^2,6.0^5,14.0^7,12.0^9,13]tetradecaphosphane. When crystallizing 1 pure 1a precipitates, which at +10°C in solution is retransformed into the isomeric mixture 1a , 1b , 1c by inversion of the configuration.     

Beiträge zur Chemie des Phosphors. 222. Pentaisopropyl-tridecaphosphan(5), P13i-Pr5– Struktur in Lösung und im Kristall

Contributions to the Chemistry of Phosphorus. 222. Pentaisopropyltridecaphosphane(5), P₁₃iPr₅ – Structure in Solution and in the Crystal In an earlier investigation [3] pentaisopropyltridecaphosphane(5) ( 1 ) had been obtained by reacting i-PrPCl₂, P₄ and magnesium and subsequently thermolysing the crude reaction product, but had been structurally characterized only incompletely. We have now corroborated the earlier postulated constitution by NMR spectroscopic studies and an X-ray structural analysis. Thus 1 is 3,4,7,10,11-pentaisopropyl-pentacyclo[7.4.0.0^2,6.0^5,13.0^8,12]tridecaphosphane. In solution two configurational isomers 1 a and 1 b exist in the relative abundance of about 2 : 1, which have the symmetry C₁ and C_s, respectively. When crystallizing pure 1 b precipitates, which at room temperature in solution is retransformed into the isomeric mixture 1 a , 1 b by inversion of the configuration. Any indications of an additional symmetric diastereomer have not been found. Obviously, in isomer 1 b the inversion barrier of the atom P⁷ is markedly higher than for the atoms of the two-atom bridges P³? P⁴ and P¹⁰? P¹¹, respectively.     

Beiträge zur Chemie des Phosphors. 163. Zur Kenntnis der Triorgano-nonaphosphane(3) P9Et3 und P9(t-Bu)3; erster Nachweis der Inversion in einem Polycyclophosphan

Contributions to the Chemistry of Phosphorus. 163. About the Triorgano-nonaphosphanes(3) P₉Et₃ and P₉(t-Bu)₃; the First Detection of the Inversion of Configuration in a Polycyclophosphane Triethyl-nonaphosphane(3) ( 1 ) and tri-tert-butyl-nonaphosphane(3) ( 2 ) have been obtained by thermolysis and by dehalogenating a mixture of t-BuPCl₂ and PCl₃, respectively, and have been isolated in pure form. According to a complete analysis of their ³¹P{¹H} NMR spectra 1 and 2 possess a P₉ skeleton analogous to that of deltacyclane, thus being 5,8,9-triorgano-tetracyclo[4.3.0.0.^2,4.0^3,7]nonaphosphanes. In each case the experimental spectrum can be simulated quite satisfactorily by the superposition of the spectra of two configurational isomers a and b , which differ in their relative arrangements of the substituents. When crystallizing 2 under proper conditions (?30°C) pure 2a precipitates, which on heating in solution is retransformed into the isomeric mixture 2a , 2b byinversion of the configuration. The dominating process therein is the change of configuration at P⁵; besides a quasi synchronous inversion occurs at P⁸, P⁹ and possibly also at P⁵, P⁸, P⁹, as is evident from the 2-D ³¹P NMR exchange spectrum. The same inversion processes also take place in 1 even though at a lower rate.     

Beiträge zur Chemie des Phosphors. 219 [1]. Tetraisopropyl-octadecaphosphan(4), P18i-Pr4 – Darstellung und kernresonanzspektroskopische Strukturbestimmung

Contributions to the Chemistry of Phosphorus. 219. Tetraisopropyloctadecaphosphane(4), P₁₈i-Pr₄ — Preparation and Structure Determination by Nuclear Magnetic Resonance Tetraisopropyloctadecaphosphane(4) ( 1 ) has been obtained by reaction of i-PrPCl₂ with P₄ and magnesium and subsequent thermolysis of the crude reaction product, and has been isolated in 95% purity. According to NMR-spectroscopic investigations, 1 contains a conjuncto-phosphane skeleton consisting of a P₁₁(5)- and a P₉(3)-structural element analogous to that of deltacyclane, joined through a common P₂-bridge. Thus, 1 is 8,14,16, 18-tetraisopropyloctacyclo[13.2.1.0^2,13.0^3,11.0^4,9.0^5,7.0^6,10.0^12,17]octadecaphosphane. Compound 1 is formed as a mixture of two configurational isomers 1 a and 1 b , which differ from each other in their spatial arrangements of the isopropyl group at P₈.     

Beiträge zur Chemie des Phosphors. 223. Hexaisopropyl-icosaphosphan(6), P20i-Pr6 — Darstellung und kernresonanz-spektroskopische Strukturbestimmung von zwei Konstitutionsisomeren

Contributions to the Chemistry of Phosphorus. 223. Hexaisopropylicosaphosphane(6), P₂₀i? Pr₆ — Preparation and Structure Determination of Two Constitutional Isomers by Nuclear Magnetic Resonance Hexaisopropyl-icosaphosphane(6) has been obtained by reaction of i-PrPCl₂ with P₄ and magnesium and subsequent thermolysis of the crude reaction product. The compound is formed as a mixture of two constitutional isomers 1 and 2 of equal abundance, which have been almost purely isolated by HPLC as a mixture of the diastereomers 1 a , 1 b and in the form of the separate configurational isomers 2 a and 2 b , respectively. According to NMR-spectroscopic investigations, the new conjuncto-phosphane skeletons of 1 and 2 consist of a P₁₃(5)- and a P₉(5)-structural element analogous to that of brexane and of two P₁₁(5)-partial skeletons, respectively, joined in each case through a common P₂-bridge. Thus, 1 is 6,7,9,16,17,20-hexaisopropyloctacyclo[10.8.0.0^2,14.0^3,11.0^4,8.0^5,10.0^13,18.0^15,19]icosaphosphane and 2 is 7,9,15,17,19,20-hexaisopropyl-octacyclo[14.2.1.1^5,8.0^2,14.0^3,12.0^4,10.0^6,11.0^13,18]icosaphosphane. The phosphorus hydrogen compound P₂₀H₆ [22, 2c] should exhibit the same constitutional isomerism.     

Beiträge zur Strukturchemie phosphorhaltiger Ketten und Ringe. 16. Die Molekül- und Kristallstruktur des Triisopropyl-undecaphosphans P11(i-Pr)3

Structural Chemistry of Phosphorus Containing Chains and Rings. 16. Molecular and Crystal Structure of the Triisopropylundecaphosphane P₁₁(i-Pr)₃ The compound 4,7,11-triisopropyl-pentacyclo[6.3.0.0^2.6.0^3.10.0^5.9]undecaphosphane, C₉H₂₁P₁₁, crystallizes triclinically in the space group P1 with a = 1 045.3 pm, b = 1 057.2 pm, c = 1 075,0 pm, α = 101.00°, β = 98.89°, γ = 112.27° and Z = 2. The main structural feature is a phosphorus skeleton with approximate symmetry D₃ composed of six five-membered rings which are asymmetrically substituted by the isopropyl groups. The (average) bond lengths are d(P? P) = 221.6 pm, d(P? C) = 187.5 pm, d(C? C) = 151.4 pm, d(C? H) = 108 pm with 217.6 ≤ d(P? P) ≤ 226.4 pm. The geometry of the substituents is quite normal.     

Beiträge zur Chemie des Phosphors. 217 [1]. Hexaisopropyl-octadecaphosphan(6), P18i-Pr6—Darstellung und kernresonanzspektroskopische Strukturbestimmung

Contributions to the Chemistry of Phosphorus. 217. Hexaisopropyloctadecaphosphane(6), P₁₈i-Pr₆ – Preparation and Structure Determination by Nuclear Magnetic Resonance Hexaisopropyl-octadecaphosphane(6) ( 1 ) has been obtained by reaction of i-PrPCl₂ with P₄ and magnesium and subsequent thermolysis of the crude reaction product, and has been purely isolated as a yellow solid. According to NMR-spectroscopic investigations, 1 contains a new conjuncto-phosphate skeleton consisting of a P₁₁(5)- and a P₉(5)-structural element analogous to that of brexane, joined through a common P₂-bridge. Thus, 1 is 5,7,8,14,16,18-hexaisopropyl-heptacyclo[13.2.1.0^2,13.0^3,11.0^4,9.0^6,10.0^12,17]octadecaphosphane. Compound 1 is formed as a mixture of two configurational isomers 1a and 1b , which probably differ from each other by inversion of the configuration at the (PR)₂-bridge of the P₉(5) partial structure analogous to that of brexane.     

Synthese und dynamisches Verhalten von [Rh2(μ-H)3H2(PiPr3)4]+. Beiträge zur Reaktivität des Tetrahydridodirhodium-Komplexes [Rh2H4(PiPr3)4]

Synthesis and Dynamic Behaviour of [Rh₂(μ-H)₃H₂(PiPr₃)₄]⁺. Contributions to the Reactivity of the Tetrahydridodirhodium Complex [Rh₂H₄(PiPr₃)₄] An improved synthesis of [Rh₂H₄(PiPr₃)₄] ( 2 ) from [Rh(η³-C₃H₅)(PiPr₃)₂] ( 1 ) or [Rh(η³-CH₂C₆H₅)(PiPr₃)₂] ( 3 ) and H₂ is described. Compound 2 reacts with CO or CH₃OH to give trans-[RhH(CO)(PiPr₃)₂] ( 4 ) and with ethene/acetone to yield a mixture of 4 and trans-[RhCH₃(CO)(PiPr₃)₂] ( 5 ). The carbonyl(methyl) complex 5 has also been prepared from trans-[RhCl(CO)(PiPr₃)₂] ( 6 ) and CH₃MgI. Whereas the reaction of 2 with two parts of CF₃CO₂H leads to [RhH₂(η²-O₂CCF₃) · (PiPr₃)₂] ( 8 ), treatment of 2 with one equivalent of CF₃CO₂H in presence of NH₄PF₆ gives the dinuclear compound [Rh₂H₅(PiPr₃)₄]PF₆ ( 9a ). The reactions of 2 with HBF₄ and [NO]BF₄ afford the complexes [Rh₂H₅(PiPr₃)₄]BF₄ ( 9b ) and trans-[RhF(NO)(PiPr₃)₂]BF₄ ( 11 ), respectively. In solution, the cation [Rh₂(μ-H)₃H₂(PiPr₃)₄]⁺ of the compounds 9a and 9b undergoes an intramolecular rearrangement in which the bridging hydrido and the phosphane ligands are involved.     

Reaktive E = C(p-p)π-Systeme. XLII [1]. Neue Koordinationsverbindungen des 2-(Diisopropylamino)-1-phosphaethins: [{η4-(iPr2NCP)2}Ni{η2-(iPr2NCP)}], [(Ph3P)2Pt{η2-(iPr2NCP)}] und [Co2(CO)6{η2-η2-(iPr2NCP)}]

Reactive E = C(pp)π-Systems. XLII [1]. Novel Coordination Compounds of 2-(Diisopropylamino)-1-phosphaethyne: [{η⁴-(iPr₂NCP)₂}Ni{η²-(iPr₂NCP)}], [(Ph₃P)₂Pt{η²-(iPr₂NCP)}], and [Co₂(CO)₆{η²-μ²-(iPr₂NCP)}] 2-(Diisopropylamino)-phosphaethyne iPr₂N? C?P ( 2 ) reacts with the Ni(0)-complexes [Ni(1,5-cyclooctadiene)₂] and [Ni(CO)₃(1-azabicyclo[2.2.2]octane)], respectively, to give the novel complex [{η⁴-(iPr₂NCP)₂}Ni{η²-(iPr₂NCP)}] ( 5 ), with the 1,3-diphosphacyclobutadiene derivative and 2 (side-on) as π-ligands. The molecular structure of 5 determined by X-ray diffraction on single crystals proves the spin systems and rotational barriers deduced from NMR-data (¹H, ¹³C-, ³¹P). The PC distances of the four-membered ring of 1.817(2) and 1.818(2) Å – as expected – are considerably longer than the PC bond of the η²-coordinated phosphaalkyne 2 [1.671(2) Å]. – In the reactions of 2 with [(Ph₃P)₂Pt(C₂H₄)] or [Co₂(CO)₈] the ligand properties of 2 resemble those of alkynes affording the complexes [(Ph₃P)₂Pt{η²-(iPr₂NCP)}] ( 7 ) with side-on coordinated 2 and [Co₂(CO)₆{η²-μ²-(iPr₂NCP)}] with 2 acting as a 4e donor bridge in quantitative yield. In attempts to prepare copper(I) complexes of the aminophosphaalkyne 2 by reaction with CuCl or CuI the only isolable product formed in reasonable amounts under the influence of air and moisture is the 1 λ³, 3 λ⁵-diphosphetene (iPr₂N) ( 10 ) (isolated yield: ca. 20%). The crystal structure analysis of 10 indicates a strong structural relationship to the diamino-2-phosphaallyl cation [Me(iPr₂N)]⁺ ( 12 ), the 1,3-diphosphacyclobutadiene ligand (iPr₂NCP)₂ in the binuclear complex [{η¹, μ²-(iPr₂NCP)₂}Ni₂(CO)₆] ( 3a ) as well as to the heterocycles (dme)₂LiOE₂′ (E′ = S, 11a ; E′ = Se, 11b ) prepared by Becker et al. [11b, 35].     

Beiträge zur Chemie des Phosphors. 212. Tetraisopropyl-dodecaphosphan(4), P12i-Pr4 – Darstellung,Eigenschaften und Moleküldynamik

Contributions to the Chemistry of Phosphorus. 212. Tetraisopropyldodecaphosphane(4), P₁₂i-Pr₄ – Preparation, Properties, and Molecular Dynamics According to an earlier crystal structure analysis, tetraisopropyldodecaphosphane(4) ( 1 ) exhibits the symmetry C₂, and the substituents are arranged in all-trans position [3]. We have now found by NMR spectroscopic studies that in solution a second configurational isomer of the symmetry C_S ( 1b ) exists in addition to the molecule present in the crystal ( 1a ). The transformation of 1a into 1b , which can only occur through a quasi synchronous inversion at the atoms P³ and P⁴ or P⁹ and P¹⁰, takes place at a noticeable rate already below room temperature.     

Binding H2, N2, H-, and BH3 to transition-metal sulfur sites: synthesis and properties of [RuL(PR3)(N2Me2S2)] Complexes (L=eta2-H2, H-, BH3; R=Cy, iPr)

The reactions of [Ru(N₂)(PR₃)(‘N₂Me₂S₂’)] [‘N₂Me₂S₂’=1,2‐ethanediamine‐N,N′‐dimethyl‐N,N′‐bis(2‐benzenethiolate)(2?)] [ 1 a (R=iPr), 1 b (R=Cy)] and [μ‐N₂{Ru(N₂)(PiPr₃)(‘N₂Me₂S₂’)}₂] ( 1 c ) with H₂, NaBH₄, and NBu₄BH₄, intended to reduce the N₂ ligands, led to substitution of N₂ and formation of the new complexes [Ru(H₂)(PR₃)(‘N₂Me₂S₂’)] [ 2 a (R=iPr), 2 b (R=Cy)], [Ru(BH₃)(PR₃)(‘N₂Me₂S₂’)] [ 3 a (R=iPr), 3 b (R=Cy)], and [Ru(H)(PR₃)(‘N₂Me₂S₂’)]^? [ 4 a (R=iPr), 4 b (R=Cy)]. The BH₃ and hydride complexes 3 a , 3 b , 4 a , and 4 b were obtained subsequently by rational synthesis from 1 a or 1 b and BH₃?THF or LiBEt₃H. The primary step in all reactions probably is the dissociation of N₂ from the N₂ complexes to give coordinatively unsaturated [Ru(PR₃)(‘N₂Me₂S₂’)] fragments that add H₂, BH₄^?, BH₃, or H^?. All complexes were completely characterized by elemental analysis and common spectroscopic methods. The molecular structures of [Ru(H₂)(PR₃)(‘N₂Me₂S₂’)] [ 2 a (R=iPr), 2 b (R=Cy)], [Ru(BH₃)(PiPr₃)(‘N₂Me₂S₂’)] ( 3 a ), [Li(THF)₂][Ru(H)(PiPr₃)(‘N₂Me₂S₂’)] ([Li(THF)₂]‐ 4 a ), and NBu₄[Ru(H)(PCy₃)(‘N₂Me₂S₂’)] (NBu₄‐ 4 b ) were determined by X‐ray crystal structure analysis. Measurements of the NMR relaxation time T₁ corroborated the η² bonding mode of the H₂ ligands in 2 a (T₁=35 ms) and 2 b (T₁=21 ms). The H,D coupling constants of the analogous HD complexes HD‐ 2 a (¹J(H,D)=26.0 Hz) and HD‐ 2 b (¹J(H,D)=25.9 Hz) enabled calculation of the H? D distances, which agreed with the values found by X‐ray crystal structure analysis ( 2 a : 92 pm (X‐ray) versus 98 pm (calculated), 2 b : 99 versus 98 pm). The BH₃ entities in 3 a and 3 b bind to one thiolate donor of the [Ru(PR₃)(‘N₂Me₂S₂’)] fragment and through a B‐H‐Ru bond to the Ru center. The hydride complex anions 4 a and 4 b are extremely Brønsted basic and are instantanously protonated to give the η²‐H₂ complexes 2 a and 2 b .     

Kristallstruktur von (Me4N)3[Ir(SCN)6], Schwingungsspektrum und Normalkoordinatenanalyse

Crystal Structure of (Me₄N)₃[Ir(SCN)₆], Vibrational Spectra and Normal Coordinate Analysis From a mixture of the linkage isomers [Ir(NCS)_n(SCN)_6–n]^3–, n = 0–2, pure [Ir(SCN)₆]^3– has been isolated by ion exchange chromatography on diethylaminoethyl cellulose. The X-ray structure determination on a single crystal of (Me₄N)₃[Ir(SCN)₆] (trigonal, space group R3, a = 14.838(2), c = 23.827(1) Å, Z = 6) reveals the presence of two crystallographically independent complex anions which C_3i symmetry correlates with the cation/anion ratio 3 : 1. The thiocyanate ligands are exclusively S-coordinated with the average Ir–S distance of 2.384 Å and the Ir–S–C angle of 106.4°. The torsion angles S–Ir–S–C are 17.5 and 42.1°. The IR and Raman spectra of the (n-Bu₄N) salt are assigned by normal coordinate analysis based on the molecular parameters of the X-ray determination. The valence force constant f_d(IrS) is 1.57 mdyn/Å.     

Beiträge zur Chemie des Phosphors. 230. Hexaisopropyl-tetradecaphosphan(6), P14i-Pr6, und Hexaisopropyl-hexadecaphosphan(6), P16i-Pr6 — Bildung und 31P-NMR-spektroskopische Strukturbestimmung

Contributions to the Chemistry of Phosphorus. 230. Hexaisopropyltetradecaphosphane(6), P₁₄i-Pr₆, and Hexaisopropylhexadecaphosphane(6), P₁₆i-Pr₆ — Formation and Structural Determination by ³¹P-NMR Spectroscopy Hexaisopropyltetradecaphosphane(6) ( 1 ) and hexaiso-propylhexadecaphosphane(6) ( 2 ) are formed together with other isopropylpolycyclophosphanes by the reaction of i-PrPCl₂ with P₄ and magnesium and have been enriched to 30 mol% and 10 mol%, respectively. According to ³¹P-NMR spectroscopic investigations, the novel conjuncto-phosphane skeletons of 1 and 2 are the annelation products of a P₅ ring with a P₁₁(5) or a P₁₃(5) partial skeleton, respectively, joined by a common P₂ bridge. Thus, 1 is 4,5,6,10,12,14-hexaisopropylpentacyclo-[9.2.1.0^2,9 .0^3,7 .0^8,13]tetradecaphosphane and 2 is 5,6,7,11,14,15-hexaisopropylhexacyclo[7.7.0.0^2,13 .0^3,10 .0^4,8 .0^12,16]hexadecaphosphane. The phosphorus hydrides P₁₄H₁₆ and P₁₆H₆ have the same skeletal structures which are also intermediate stages in the formation of Hittorf's phosphorus.     

Hydrothermal Synthesis,Structure, and Optical Properties of Two Nanosized Ln26@CO3 (Ln=Dy and Tb) Cluster‐Based Lanthanide–Transition‐Metal–Organic Frameworks (Ln MOFs)

Two Ln₂₆@CO₃ (Ln=Dy and Tb) cluster‐based lanthanide–transition‐metal–organic frameworks (Ln MOFs) formulated as [Dy₂₆Cu₃(Nic)₂₄(CH₃COO)₈(CO₃)₁₁(OH)₂₆(H₂O)₁₄]Cl ? 3 H₂O ( 1 ; HNic=nicotinic acid) and [Tb₂₆NaAg₃(Nic)₂₇(CH₃COO)₆(CO₃)₁₁(OH)₂₆Cl(H₂O)₁₅] ? 7.5 H₂O ( 2 ) have been successfully synthesized by hydrothermal methods and characterized by IR, thermogravimetric analysis (TGA), elemental analysis, and single X‐ray diffraction. Compound 1 crystallizes in the monoclinic space group Cc with a=35.775(12) Å, b=33.346(11) Å, c=24.424(8) Å, β=93.993(5)°, V=29065(16) ų, whereas 2 crystallizes in the triclinic space group P with a=20.4929(19) Å, b=24.671(2) Å, c=29.727(3) Å, α=81.9990(10)°, β=88.0830(10)°, γ=89.9940(10)°, V=14875(2) ų. Structural analysis indicates the framework of 1 is a 3D perovskite‐like structure constructed out of CO₃@Dy₂₆ building units and Cu⁺ centers by means of nicotinic acid ligand bridging. In 2 , however, nanosized CO₃@Tb₂₆ units and [Ag₃Cl]²⁺ centers are connected by Nic^? bridges to give rise to a 2D structure. It is worth mentioning that this kind of 4d–4f cluster‐based MOF is quite rare as most of the reported analogous compounds are 3d–4f ones. Additionally, the solid‐state emission spectra of pure compound 2 at room temperature suggest an efficient energy transfer from the ligand Nic^? to Tb³⁺ ions, which we called the “antenna effect”. Compound 2 shows a good two‐photon absorption (TPA) with a TPA coefficient of 0.06947 cm GM^?1 (1 GM=10^?50 cm⁴ s photon^?1), which indicates that compound 2 might be a good choice for third‐order nonlinear optical materials.     

Synthese,Kristallstrukturen und quantenchemische Untersuchung von Verbindungen mit leiterartigem Al4P4‐ und hexagonal prismatischem Al6P6‐Grundgerüst

The reaction of AlCl₃ with Li₂PR (R = SiiPr₃, SiMeiPr₂) in a mixture of heptane and ether yields in the polycyclic compounds [(AlCl)₄(μ₃‐PR)₂(μ‐PR)₂(Et₂O)₂]( 1a : R = SiiPr₃; 1b : SiMeiPr₂) with a ladder‐shaped Al₄P₄ core. The coordination sphere of the outer aluminium atoms in these compounds is completed by ether ligands. In contrast, the reaction of AlCl₃ with Li₂PSiiPr₃ in pure heptane yields in the formation of the hexagonal prismatic compound [(AlCl)₆(μ₃‐PSiiPr₃)₆]( 2 ). 1 and 2 were characterized by single crystal X‐ray diffraction analysis as well as by ³¹P{1H} and ²⁷Al NMR spectroscopy. The structure determining effect of the solvent can be rationalized by quantumchemical calculations, which also show that the hexagonal prismatic structure is the most stable of the investigated oligomers in absence of ether.     

α‐Tetraphosphorus Trichalcogenide Diamides and Imides containing both Sulfur and Selenium

Reaction of a mixture of bicyclic phosphorus sulfide selenide iodides α‐P₄S_nSe_3−nI₂ (n = 0–3) with PrⁱNH₂ and Et₃N gave corresponding diamides α‐P₄S_nSe_3−n(NHPrⁱ)₂ (n = 0–3) and imides α‐P₄S_nSe_3−n(μ‐NPrⁱ) (n = 2–3), identified in solution by ³¹P NMR. In one isomer of α‐P₄S₂Se(μ‐NPrⁱ), the C₂ symmetry of imides such as α‐P₄S₃(μ‐NPrⁱ) was broken, allowing relative assignment of ²J NMR couplings to the PNP bridge and the PSP bridge opposite to it. The coupling through the sulfur bridge was found to be reduced to ca. zero, in contrast to previous assumptions for this class of compounds. Ab initio models were calculated at the MPW1PW91/svp level for the sulfide selenide imides and for a selection of bond rotamers of the diamides, and at the MPW1PW91/LanL2DZ(d) level for the sulfide selenide diiodides. Different skeletal isomers were prevalent for the mixed chalcogenide diamides than for the diiodides, showing that exchange of chalcogen between skeletal positions took place in the amination reaction even at room temperature. Similar differences to those observed were predicted by the models, suggesting that equilibrium was attained.     

Beiträge zur Kristallchemie und zum thermischen Verhalten von wasserfreien Phosphaten. XXXIII [1] In2P2O7, ein Indium(I)‐diphosphato‐indat(III) und In4(P2O7)3 — Darstellung,Kristallisation und Kristallstrukturen

Contributions on Crystal Chemistry and Thermal Behaviour of Anhydrous Phosphates. XXXIII [1] In₂P₂O₇ an Indium(I)‐diphosphatoindate(III), and In₄(P₂O₇)₃ — Synthesis, Crystallization, and Crystal Structure Solid state reactions via the gas phase lead to the new mixed‐valence indium(I, III)‐diphosphate In₂P₂O₇. Colourless single crystals of In₂P₂O₇ have been grown by isothermal heating of stoichiometric amounts of InPO₄ and InP (800 °C; 7d) using iodine as mineralizer. The structure of In₂P₂O₇ [P2₁/c, a = 7.550(1) Å, b = 10.412(1) Å, c = 8.461(2) Å, b = 105.82(1)°, 2813 independent reflections, 101 parameter, R1 = 0.031, wR2 = 0.078] is the first example for an In⁺ cation in pure oxygen coordination. Observed distances d(In^I‐O) are exceptionally long (d_min(In^I‐O) = 2.82 Å) and support assumption of mainly s‐character for the lone‐pair at the In⁺ ion. Single crystals of In₄(P₂O₇)₃ were grown by chemical vapour transport experiments in a temperature gradient (1000 → 900 °C) using P/I mixtures as transport agent. In contrast to the isostructural diphosphates M₄(P₂O₇)₃ (M = V, Cr, Fe) monoclinic instead of orthorhombic symmetry has been found for In₄(P₂O₇)₃ [P2₁/a, a = 13.248(3) Å, b = 9.758(1) Å, c = 13.442(2) Å, b = 108.94(1)°, 7221 independent reflexes, 281 parameter, R1 = 0.027, wR2 = 0.067].     

Untersuchungen über Zinn(IV)-alkoxide. II. Isolierung und Charakterisierung der Verbindung Sn3O(OiBu)10 · 2i-BuOH. Das erste Beispiel für ein partielles Hydrolyseprodukt eines Zinn(IV)-alkoxids

Investigations into Tin(IV) Alkoxides. II. Isolation and Characterization of the Compound Sn₃O(OⁱBu)₁₀₁₀ · 2i-BuOH. The First Example of a Partially Hydrolized Tin(IV) Alkoxide The partial hydrolysis product Sn₃O(OⁱBu)₁₀ · 2i-BuOH was obtained by slow hydrolysis of the reaction product of tin tetrachloride with sodium isobutoxide. The compound forms colourless, moisture sensitive crystals, which easily release the coordinated solvent molecules in dry air. Its crystal and molecular structure has been determinated by single crystal X-ray diffraction. The compound crystallizes in the triclinic space group P1 with a = 1363.5(7), b = 1462.7(10), c = 1637.7(7) pm, α = 95.40(5)°, β = 96.79(4)°, γ = 102.12(5)° and Z = 2. The crystal structure consists of discrete, trimeric molecules with octahedrally coordinated tin atoms which are connected to each other corresponding to the formulation Sn₃(μ₃-O)(μ₂-OⁱBu)₃(O¹Bu)₇ · (i-BuOH)₂ by three isobutoxide groups bridging two metal atoms and a single threefold bridging oxygen atom     

Vinyliden-Übergangsmetallkomplexe XXVI. Synthese und struktur kationischer Carbonyl-, Alken-, Vinyliden-, Alkinyl- und Alkin-Rhodiumkomplexe mit der Baueinheit trans-[Rh(PPr3)2]

The complex trans-[Rh(CO)(NH₃)(PiPr₃)₂]PF₆ (2) was prepared from [(η³-C₃H₅)Rh(PⁱPr₃)₂] (1), NH₄PF₆ and CO or from 1 and NH₄PF₆ in presence of an excess of methanol. With an excess of CO, the dicarbonyl and tricarbonyl compounds trans-[Rh(CO)₂(PⁱPr₃)₂]PF₆ (3) and [Rh(CO)₃(PⁱPr₃)₂]PF₆ (4) were obtained. Displacement of one CO ligand in 3 by pyridine and acetone led to the formation of trans-[Rh(CO)(py)PⁱPr₃)₂]PF₆ (5a) and trans-[Rh(CO) (O=CMe₂(PⁱPr₃)₂]PF₆ (6), respectively. Treatment of 1 with [pyH]BF₄ and pyridine gave trans-[Rh(py)₂(PⁱPr₃)₂]BF₄ (7); in presence of H₂ the dihydrido complex [RhH₂(py)₂(PⁱPr₃)₂]BF₄ (8) was formed. The reaction of 1 with NH₄PF₆ and ethylene produced trans [Rh(C₂H₄(NH₃(PⁱPr₃)₂]PF₆(9) whereas with methylvinylketone and acetophenone the octahedral hydridorhodium(III) complexes [RhH(η²-CH=CHC(=O)CH₃ (NH₃(PⁱPr₃)₂]PF₆(11) and [RhH(η2-C₆H₄C(=O)CH₃(NH₃(Pⁱpr₃)₂]PF₆ (13) were obtained. The synthesis of the cationic vinylidenerhodium(I) compounds trans-[Rh(=C=CHR)(py)(PⁱPr₃)₂]BF₄ (14–16) and trans-[Rh(=C=CHR)(NH₃)(PⁱPr₃) ₂]PF6 (17–19) was achieved either on treatment of 1 with [pyH]BF₄ or NH₄PF₆ in presence of 1-alkynes or by ethylene displacement from 9 by HCCR. With tert-butylacetylene as substrate, the alkinyl(hydrido)rhodium(III) complex [RhH(CC^tBu)(NH₃)(O=CMe₂)(PⁱPr₃) ₂]PF₆ (20) was isolated which in CH₂Cl₂ solution smoothly reacted to give 19 (R =^tBu). The cationic but-2-yne compound trans-[Rh(MeCCMe)(NH₃)(Pⁱ Pr₃)₂]PF₆ (21) was prepared from 1, NH₄PF₆ and C₂Me₂. The molecular structures of 3 and 14 were determined by X-ray crystallography; in both cases the square-planar coordination around the metal and the trans disposition of the phosphine ligands was confirmed.

Abstract

Der Komplex trans-[Rh(CO)(NH₃)(PⁱPr₃)₂]PF₆ (2) wurde aus [(η³-C₃H₅)Rh(PⁱPr₃)₂] (1), NH₄PF₆ und CO oder aus 1, NH₄PF₆ und Methanol hergestellt. In Gegenwart von überschüssigem CO wurden die Dicarbonyl- und Tricarbonyl-Verbindungen trans-[Rh(CO)₂(PⁱPr₃)₂]PF₆ (3) und [Rh(CO)₃(PⁱPr₃)₂]PF₆ (4) erhalten. Die Verdrängung eines CO-Liganden in 3 durch Pyridin oder Aceton führte zur Bildung von trans-[Rh(CO)(py)(PⁱPr₃)₂]PF₆ (5a) bzw. trans-[Rh(CO)(O=CMe₂)(PⁱPr₃)₂]PF₆ (6). Bei Einwirkung von [pyH]BF₄ und Pyridin auf 1 entstand trans-[Rh(py)₂(PⁱPr₃)₂]BF₄ (7); in Gegenwart von H₂ bildete sich der Dihydrido-Komplex [RhH₂(py)₂(PⁱPr₃) ₂]BF₄ (8). Die Reaktion von 1 mit NH₄PF₆ und Ethen lieferte trans-[Rh(C₂H₄)(NH₃)(PⁱPr₃)₂] PF₆ (9) während mit Methylvinylketon und Acetophenon die oktaedrischen Hydridorhodium(III)-Komplexe [RhH(η²-CH=CHC(=O)CH₃ (NH₃)-(PⁱPr₃)₂]PF₆ (11) und [RhH(η-²-C₆H₄C(=O)CH₃(NH₃)(PⁱPr₃)₂)₂]PF₆ (13) erhalten wurden. Die Synthese der kationischen Vinyli-denrhodium(I)-Verbindungen trans-[Rh(=C=CHR(py)(PⁱPr₃)₂]BF₄ (14–16) und trans-[Rh(=C=CHR)(NH₃)(PⁱPr₃)₂]PF₆ (17–19) gelang durch Einwirkung von [pyH]BF₄ bzw. NH₄PF₆ auf 1 in Gegenwart von 1-Alkinen oder durch Ethen-Verdrängung aus 9 mit HCCR. Mit tert-Butylacetylen als Reaktionspartner wurde der Alkinyl(hydrido)rhodium(III)-Komplex [RhH(CC^tBu)(NH₃(O=CMe₂)(PⁱPr₃)₂]PF₆ (20) isoliert, der in CH₂Cl₂-Lösung sofort zu 19 (R =^tBu) reagiert. Die kationische 2-Butin-Verbindung trans -[Rh(MeCCMe)(NH₃)PⁱPr₃)₂]PF₆ (21) wurde aus 1, NH₄PF₆ und C₂Me₂ hergestellt. Die Strukturen von 3 und 14 wurden kristallographisch bestimmt; in beiden Fa len ließ sich die quadratisch-planare Koordination des Metalls und die trans-Anordnung der Phosphanliganden bestätigen.     

Neue Kupferkomplexe mit Phosphaalkenliganden. Molekülstruktur von [Cu{P(Mes*)C(NMe2)2}2]BF4 (Mes* = 2,4,6‐tBu3C6H2)

New Copper Complexes Containing Phosphaalkene Ligands. Molecular Structure of [Cu{P(Mes*)C(NMe₂)₂}₂]BF₄ (Mes* = 2,4,6‐tBu₃C₆H₂) Reaction of equimolar amounts of the inversely polarized phosphaalkene tBuP=C(NMe₂)₂ ( 1a ) and copper(I) bromide or copper(I) iodide, respectively, affords complexes [Cu₃X₃{μ‐P(tBu)C(NMe₂)₂}₃] ( 2 ) (X =Br) and ( 3 ) (X = I) as the formal result of the cyclotrimerization of a 1:1‐adduct. Treatment of 1a with [Cu(L)Cl] (L = PiPr₃; SbiPr₃) leads to the formation of compounds [CuCl(L){P(tBu)C(NMe₂)₂}] ( 4a ) (L = PiPr₃) and ( 4b ) (L = SbiPr₃), respectively. Reaction of [(MeCN)₄Cu]BF₄ with two equivalents of PhP=C(NMe₂)₂ ( 1b ) yields complex [Cu{P(Ph)C(NMe₂)₂}₂]BF₄ ( 5b ). Similarly, compounds [Cu{P(Aryl)C(NMe₂)₂}₂]BF₄ ( 5c (Aryl = Mes and 5d (Aryl = Mes*)) are obtained from ArylP=C(NMe₂)₂ ( 1c : Aryl = Mes; 1d : Mes*) and [(MeCN)₄Cu]BF₄ in the presence of SbiPr₃. Complexes 2 , 3 , 4a , 4b , and 5b‐5d are characterized by means of elemental analyses and spectroscopy (¹H‐, ¹³C{¹H}‐, ³¹P{¹H}‐NMR). The molecular structure of 5d is determined by X‐ray diffraction analysis.