Zur Reaktion der Lanthanoiden mit Chelatliganden Darstellung und Struktur von [(py2CH)3Gd]

On the Reaction of the Lanthanides with Chelate Ligands Synthesis and Crystal Structure of [(py₂CH)₃Gd] GdBr₃ reacts with [(py₂CH)Li] to the mononuclear complex [(py₂CH)₃Gd] 1 . The structure of 1 was characterized by X-ray single crystal structure analysis. Space group P2₁, Z = 2, a = 951.4(10) pm, b = 1369.4(10) pm, c = 1074.5(10) pm, β = 105.69(8)°. The Gd-Ion is surrounded by the six nitrogen atoms of the three chelate ligands and shows a distorted trigonal prismatic coordination. As a difference to the lithium salt of the ligand, the six-membered metalla-cycles in 1 are not planar, but show a boat conformation.     

Die Reaktion von tBu2P‐P=P(Me)tBu2 mit [Fe2(CO)9] und [(η2‐C8H14)2Fe(CO)3]

^tBu₂P‐P=P(Me)^tBu₂ reacts with [Fe₂(CO)₉] to give [μ‐(1, 2, 3:4‐η‐^tBu₂P¹‐P²‐P³‐P^4tBu₂){Fe(CO)₃}{Fe(CO)₄}] ( 1 ) and [trans‐(^tBu₂MeP)₂Fe(CO)₃]( 2 ). With [(η²‐C₈H₁₄)₂Fe(CO)₃] in addition to [μ‐(1, 2, 3:4‐η‐^tBu₂P¹‐P²‐P³‐P^4tBu₂){Fe(CO)₂PMe^tBu₂}‐{Fe(CO)₄}] ( 10 ) and 2 also [(μ‐P^tBu₂){μ‐P‐Fe(CO)₃‐PMe^tBu₂}‐{Fe(CO)₃}₂(Fe‐Fe)]( 9 ) is formed. 1 crystallizes in the monoclinic space group P2₁/c with a = 875.0(2), b = 1073.2(2), c = 3162.6(6) pm and β = 94.64(3)?. 2 crystallizes in the monoclinic space group P2₁/c with a = 1643.4(7), b = 1240.29(6), c = 2667.0(5) pm and β = 97.42(2)?. 9 crystallizes in the monoclinic space group P2₁/n with a = 1407.5(5), b = 1649.7(5), c = 1557.9(16) pm and β = 112.87(2)?.     

Zur Reaktion von 1,4-Pentadien-3-onen mit Phenylacetonitrilen

Diarylpentadienones (1) react with phenylacetonitriles (2) to give 4-oxo-1.2.6-triaryl-cyclohexane-1-nitrils (4). Isomer compounds (6) may be obtained byMichael addition of2 to esters of cinnamic acids and cyclisation to5, followed by hydrolysis and decarboxylation. The steric behaviour of4 and6 is established by¹H- and¹³C-NMR-spectroscopy and by the different mode of reaction and products in the condensation of4 and6 with aromatic aldehydes to give8 or9.     

Zur Reaktion von 1,4-Pentadien-3-onen mit Malonestern

Zusammenfassung Diarylpentadienone (1) ergeben mit Malonester (2) entweder 2,6-Diaryl-4-oxo-5-hexen-1,1-dicarbonsäurediester (3) oder 2,6-Diaryl-4-oxo-cyclohexan-1,10dicarbonsäurediester (5). Das sterische Verhalten von3 und5 wird durch IR- und NMR-Untersuchungen ermittelt sowie die sterischen Gesichtspunkte der Gesamtreaktion diskutiert. Weiter werden die Bedingungen zur Darstellung — besonders die Verwendbarkeit verschiedener basischer Katalysatoren — untersucht.

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On the reactions of 1.4-pentadien-3-ones with malonates

Diarylpentadienones (1) react easily with malonates (2) to give diesters of 2.6-diaryl-4-oxo-5-hexen-1.1-dicarboxylic acids (3) and of 2.6-diaryl-4-oxo-cyclohexane-1.1-dicarboxylic acids (5), resp. The steric behaviour of3 and5 is established by IR- and NMR-spectroscopy and the influence of some basic catalysts on the reaction products is discussed.

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Mit 2 Abbildungen

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Auszugsweise vorgetragen anläßlich der 75-Jahr-Feier des VöCh, Wien, 17. bis 20. Mai 1972.     

Synthese und Kristallstruktur von [C(NMe2)3]2[(CO)4Fe(μ‐InCl2)2Fe(CO)4]

Synthesis and Crystal Structure of [C(NMe₂)₃]₂[(CO)₄Fe(μ‐InCl₂)₂Fe(CO)₄] Treatment of [C(NMe₂)₃]₂[(CO)₄FeInCl₃] ( 1 ) with hot water produces the dinuclear complex [C(NMe₂)₃]₂[(CO)₄Fe(μ‐InCl₂)₂Fe(CO)₄] ( 2 ) which could be crystallized from dichloromethane/pentane. 2 crystallizes in the monoclinic space group P2₁/n with a = 835.7(1), b = 1187.8(1), c = 1902.7(1) pm, β = 91.877(5)° and Z = 2. The anion contains a four‐membered Fe—In—Fe—In ring with octahedral environment at the iron atom and tetrahedral coordination at the In atom.     

Zur Reaktion von 2,2′-Dilithiumbiphenyl mit SmBr3 Die Struktur von [(C24H16)SmBr(thf)2]2 · [C24H14]

On the Reaction of Dilithiumbiphenyl with SmBr₃. The Crystal Structure of [(C₂₄H₁₆)SmBr(thf)₂]₂ · [C₂₄H₁₄] In THF SmBr₃ forms with [(biph)Li₂] the dimeric complex [(quaph)SmBr(thf)₂]₂ · [C₂₄H₁₄]. The structure was characterized by X-ray single crystal structure analysis (space group P1 (No. 2), Z = 1, a = 943.3(6) pm, b = 1 350.3(1) pm, c = 1 599.9(9) pm, α = 64.99(5)°, β = 89.02(5)°, γ = 73.02(6)°). The Sm iones are bridged by two Br iones. Coordination by one quaph and THF ligands leads to distorded octahedra coordination of the Sm iones. Additionally crystallizes one molecule dibenzonaphthacene.     

Zur Reaktion von tert-Butyl-phosphaalkin mit Molybdänkomplexen

Reaction of tert -Butyl-phosphaalkyne with Molybdenum Complexes The reaction of tBuC≡P with [(CH₃CN)₃Mo(CO)₃] leads to the complex [Mo(CO)₄〈Mo(CO)₂(η⁴-P₃CtBu){η⁴-P₂(CtBu)₂}〉] 1 as well as to the alkyne complexes [Mo(CO)₄〈{P₃(CtBu)₂}{Mo(CO)₂(CtBu)}{η³-P₂(CtBu)₂}〉] 2 and [Mo(CtBu){η⁴-P₂(CtBu)₂(CO)}{η⁵-P₃(CtBu)₂}] 3 . All compounds are characterized by X-ray structural analysis, by NMR- and IR spectroscopy and by mass spectrometry. In complex 1 a 1,3-diphosphacyclobutadiene and a 1,2,4-triphosphacyclobutadiene are connected by two molybdenum carbonyl centres. In 2 a 1,3-diphosphacyclobutadiene is π- and a novel 1,2,4-triphospholyl ligand is σ-bonded at two Mo centres. A characteristic feature of 3 besides a π co-ordinated 1,2,4-triphospholyl ligand is a 3,4-diphosphacyclopentadienone as ligand, formed via CO insertion during the cyclodimerisation of two phosphaalkynes.     

Zur Reaktion von Bis(hydroxyphenyl)methanen mit Phosphorpentachlorid — Phosphocine mit Phosphonium‐ und Phosphoranstruktur [1]

The Reaction of Bis(hydroxyphenyl)methanes with Phosphorus Pentachloride — Phosphocins with Phosphonium and Phosphorane Structure [1] Bis(2‐hydroxyphenyl)methane derivatives react with phosphorus pentachloride to give cyclic dioxaphosphocinium salts, as well as trichloro‐dioxaphosphocins. Chlorination of 6‐chloro‐dioxaphosphocins also leads to trichloro‐dioxaphosphocins. Hydrolysis of the dioxaphosphocin derivatives gives stable cyclic phosphates.     

Zur Reaktion von Phosphor(Arsen)-chalkogeniden mit Phosphor(Arsen)-triiodid

Reactions of Phosphorus(Arsenic)chalcogenides with Phosphorus(Arsenic)triiodide The specific heats and enthalpies of melting of the tetraphosphorustrithio(seleno)-diiodides have been determined. For the preparation of β-P₄S₃I₂ a new mthod by reacting P₄S₃ with PI₃ in CS₂ solution was found. Experiments to prepare compounds of the type As₄S₃I₂ by the classical methods for the preparation of the resp. phosphorus compounds failed. The reaction of As₄S₃ with AsI₃ leads to the formation of As₄S₄. The other sulphides of the As? S system As₂S₃ and As₄S₄ react with AsI₃ to AsSI, however, in the reaction of As₄S₄ the addition of S is necessary.     

Ein ungewöhnlicher trimerer Bimetallkomplex mit dem Gerüst [Zr3(μ2-OH)3(μ3-O)Li5] durch Reaktion von Zirconiumorgano- und -hydrido-Komplexen mit Wasser

An Unusual Trimeric Bimetallic Li? Zr Complex with the Backbone [Zr₃(μ₂-OH)₃(μ₃-O)Li₅] by Reaction of Zirconiumorgano and Hydrido Complexes with Water The reaction of compounds of the type [(LZr)(LiH)(L′)]_n and [(LZr)(LiH)(L′)(alkyne)]_n (L: 2,2′-Biphenolato-dianion, L′: thf, Bu₃P, alkyne: Ph? C?C? SiMe₃, CH?CH) with water at 0°C in a thf solution results in the formation of th trimeric bimetallic complex 8 [(L₂Zr)₃(μ₂-OH)₃(μ₃-O)Li₅(thf)₈(H₂O)₅] in 50% yield. The X-ray analysis of 8 shows that a planar six-membered ring Zr₃(μ₂-OH)₃ is formed. In the middle of this ring is a dianionic oxygen atom placed, coordinating to the three L₂Zr centres in a planar μ₃-coordination (bond angles 120,05μ). Five lithium ions stabilize the anionic backbone by bridging the biphenolato chelate ligands, which form seven-membered chelate rings with the atoms. ¹H-, ¹³C-, and ⁷Li-NMR spectra exhibit that the solid state structure remains unchanged in solution (thf).     

Über die Reaktion von CH3N(PCl3)(BCl3) und [(CH3)2NPCl3] [BCl4] mit AsF3

Products of the reaction between CH₃N(PCl₃)(BCl₃) and AsF₃ are BF₃, AsCl₃ and N,N′-dimethyldiazafluorophosphetidine IV. [(CH₃)₂NPCl₃][BCl₄] reacts with AsF₃ to give dimethylaminotetrafluorophosphorane VI. Preparation and NMR data of IV and VI are given.     

Zur Reaktion von Metall-koordinierten Kohlenmonoxid mit Yliden XXII. Bis(diphenylphosphino)methanid-Eisen-Komplexe Cp(L)Fe(Ph2PCHPPh2) (L = CO,Me3P)

The reaction of [Cp(CO)(dppm)Fe]BF₄ (1a) with the phosphorus ylide Me₃PCH₂ yields the novel bis(phosphino)methanideiron complex Cp(CO)Fe(Ph₂PCHPPh₂) (2), which upon photolysis in the presnece of Me₃P is converted into Cp(Me₃P)Fe(Ph₂PCHPPh₂ (3). Reaction of 2 with MeOSO₂CF₃ gives a mixture of the iron salts [(Cp(CO)Fe(Ph₂PCR(R′)PPh₂)]CF₃SO₃ (R = R′ = H (1b), R = R′ = Me (6) and R = H, R′ = Me (syn/anti-4)).     

Die darstellung von [(CH3)3PRu(CO)2Cl2]2 und [(Ch3)3P]2Ru(CO)2Cl2; Eine berichtigung zu: Die alkoholyse des triethylsilans katalysiert von [(Ch3)3P]2Ru(CO)2Cl2

The ruthenium(II) complex used as a catalyst in reactions of alcohols and Et₃SiH proved to be the dimer [(CH₃)₃PRu(CO)₂Cl₂]₂ and not the complex [(CH₃)₃P]₂ Ru(CO)₂Cl₂. Both complexes were prepared, characterized and their catalytic properties were compared.     

Zur Reaktion von Stickstoffwasserstoff bzw. Natriumazid mit Antimon(V)-chlorid

Hydrazoic acid resp. sodium azide reacts with antimony(V) chloride giving antimony tetrachlorideazide. A close examination of the reaction of hydrazoic acid and antimony(V)-chloride in dependence of the HN₃:SbCl₅ mole ratio showed that there result different reaction products in different yields. The infrared spectrum of the antimony(V) chloride addition compound of hydrazoic acid was measured and assumed.