Übergangsmetall-Komplexe des 1,1,3,3-Tetrakis(dimethylamino)-1λ5,3λ5-diphosphets

Transition Metal Complexes of 1,1,3,3-Tetrakis(dimethylamino)-1λ⁵,3λ⁵-Diphosphete 1,1,3,3-Tetrakis(dimethylamino)-1λ⁵,3aλ⁵-diphosphete, 1 , reacts with W(CO)₆ to yield the isomeric complexes {1,1,3,3-tetrakis(dimethylamino)-1λ⁵,3λ⁵-diphosphete}(pentacarbonyl)tungsten 4 and {1,1,3,3-tetrakis(dimethylamino)-1,4-dihydro-1λ⁵,3λ⁵-[1,3]diphosphetium}(pentacarbonyl)tungsten 5 . With Cr(CO)₆ the complex {1,1,3,3-tetrakis(dimethylamino)-1λ⁵,3λ⁵-diphosphete}(pentacarbonyl)chromium 6 is formed. From the reaction products of Fe₃(CO)₁₂ and Fe₂(CO)₉ with 1 the complex {1,1,3,3-tetrakis(dimethylamino)-1λ⁵,3λ⁵-diphosphete}(pentacarbonyl)iron 7 could be isolated. Properties, nmr, ir and mass spectra of the new compounds are reported. 6 and 7 were characterized by X-ray structure determinations.     

Die Reaktion von λ5-Diphospheten mit COS und CO2 Dihydro-λ5-Phosphete

Reactions of λ⁵-Diphosphetes with COS and CO₂. Dihydro-λ⁵-Phosphetes 1,1,3,3-Tetrakis(dimethylamino)-1λ⁵,3λ⁵-diphosphete, 1 , reacts with COS to yield the (3-oxo-3,4-dihydro-1λ⁵-phosphete-2-yl)-phosphonothioic bis(dimethylamide) 7 . Reaction of dimethyl substituted 1 , i.e. 1,1,3,3-tetrakis(dimethylamino)-2,4-dimethyl-1λ⁵,3λ⁵-diphosphete 4 , with COS and CO₂ results in (3-oxo-2,3-dihydro-1λ⁵-phosphete-2-yl)-phosphonothioic bis(dimethylamide) 9 , and (3-oxo-2,3-dihydro-1λ⁵-phosphete-2-yl)-phosphonic bis(dimethylamide) 10 , respectively. Reaction mechanisms are suggested. 7, 9 and 10 are characterized by their properties, and their nmr, mass-, and ir-spectra. The results of X-ray structural analyses of 9 and 10 are reported and discussed.     

Ein (Phosphonioalkinyl)- und ein Acetyl(tetracarbonyl)eisen

A (Phosphonioalkinyl)- and an Acetyl(tetracarbonyl)iron From the reaction of 1,1,3,3-tetrakis(dimethylamino)-1λ⁵,3λ⁵-diphosphete, 1 , and Fe(CO)₅ {[bis(dimethylamino)phosphoryl-methyl]-bis(dimethylamino)phosphonioethinyl}(tetracarbonyl)iron, 4 , and {1,1,3,3-tetrakis(dimethylamino)-1,4-dihydro- 1λ⁵,3λ⁵-[1,3]diphosphetium-2-carbonyl}(tetracarbonyl)-iron, 5 , can be isolated as crystalline products. The nmr, mass and ir spectra of the two compounds as well crystal and molecular structures of 4 are reported. The bonding situation in compounds 4 and 5 are discussed in detail.     

Reactions of 1,1,3,3-tetrakis(dimethylamino)-1λ5,3λ5-diphosphete with diphenylchlorophosphane and methyl iodide

1,1,3,3-Tetrakis(dimethylamino)-1λ⁵,3λ⁵-diphosphete, 1, reacts with diphenylchlorophosphane to yield 1,1,3,3-tetrakis(dimethylamino)-4-diphenylphosphanyl-1,2-dihydro-3λ⁵-[1,3]diphosphetium chloride, 2, or, depending on the reaction conditions, the isomer compound 3. The cation of 2 is deprotonated by LiN[Si(CH₃)₃]₂ to give the diphenylphosphanyl-substituted derivative of 1, i.e., compound 4. Methyl iodide adds to 1 to form 1,1,3,3-tetrakis(dimethylamino)-4-methyl-1,2-dihydro-3λ⁵-[1,3]diphosphetium iodide, 6. Deprotonation of 6 with n-butyllithium leads to the monomethyl derivative of 1, i.e., compound 7. Physical properties, NMR spectra, and mass spectra of compounds 2–4, 6, and 7 are described. The results of the X-ray structural analysis of 6 are reported and discussed. © 1996 John Wiley & Sons, Inc.     

Reaktionen des 1,1′, 3,3′-Tetrakis(dimethylamino)-1λ5, 3λ5-diphosphets mit S?H-aciden Verbindungen

Reaction of 1,′, 3,3′-Tetrakis(dimethylamino)-1λ⁵,3λ⁵-diphosphete with S? H Acidic Compounds. Reaction of 1,′,3,3′-tetrakis(dimethyl-amino)-1λ⁵,3λ⁵-diphosphete ( 1 ) with hydrogen sulfide yields bis(dimethylamino)thiophosphonylmethylidene-methyl-bis(dimethylamino)phosphorane ( 5 ).Water eliminates dimethylamine from 5 and forms bis(dimethyl-amino)thiophosphonyl-methyl(dimethylamino)phosphonylmethylene 6 . The reaction of 1 with ethylmercaptane yields the 2,4-bis(ethylthio)-derivative of 1 , i.e. compound 8 and bis(dimethylamino)phosphanylmethylidene-methyl-bis(dimethylamino)phosphorane ( 9 ), which is also formed from 1 and 2,4,6-trimethylphenylphosphane. Thiophenol protonates 1 to give the corresponding cation which is isolated as its thiophenolate, 10 . Properties, nmr and mass spectra of 5, 6 and 8 – 10 are described and discussed.     

Die Hydrolyse des 1, 1, 3, 3-Tetrakis(dimethylamino)-1λ5, 3λ5-diphosphets

Hydrolysis of 1,1,3,3-Tetrakis(dimethylamino)-1λ⁵, 3λ⁵ -diphosphete Hydrolysis of 1,1,3,3-Tetrakis(dimethylamino)-1λ⁵, 3λ⁵ -diphosphet ( 2 ) yields in the first step Bis(dimethylamino)phosphorylmethyliden-methyl-bis(dimethylamino)phosphorane ( 5 ). In the second step Bis(dimethylamino)phosphoryl-methyl(dimethylamino)phosphosphonylmethylen ( 6 ) is the main product of hydrolysis. In addition small amounts of methylphosphonic-bis(dimethylamide) ( 7 ) are formed. Properties, nmr and mass spectra of 5 and 6 are described, their mechanism of formation is discussed.     

1, 2λ5-azaphosphinines and a new 1λ5, 3λ5-. Diphosphinine

The 1,2-azaphosphinine, 9 , and the 1,3-diphosphinine, 10 , can be isolated from a mixture resulting from the reaction of 1,1,3,3-tetrakis(dimethylamino)-1λ⁵,3λ⁵-diphosphete, 1 , and ethyl isothiocyanate. The reaction of 1 with phenyl isothiocyanate yields the 1,2-azaphosphinine, 16 . Mechanisms for the formation of the compounds 9 , 10 , and 16 are suggested. The properties, the NMR, mass, and IR spectra, and the molecular and crystal structures of 9 and 10 are described and discussed.     

1,1,3,3-Tetrakis(dimethylamino)-1λ5,3λ5-diphosphet als Ligand in Koordinationsverbindungen

1,1,3,3-Tetrakis(dimethylamino)-1λ⁵,3λ⁵-diphosphete as Ligand in Coordination Compounds 1,1,3,3-Tetrakis(dimethylamino)-1λ⁵,3λ⁵-diphosphete, 1 , reacts with GeCl₂ · 1,4-dioxane, SnCl₂, and (CO)₅W(Z-cyclooctene) to give the complexes {HCP[N(CH₃)₂]₂}₂ · GeCl₂, 3 , {HCP[N(CH₃)₂]₂}₂ · SnCl₂, 4 , and {HCP[N(CH₃)₂]₂}₂ · W(CO)₅, 5 , respectively. The n.m.r., mass, and i.r. spectra of the new compounds as well as the crystal and molecular structures of 3 and 4 are reported and the bonding situation in compounds 3–5 is discussed.     

Neue 1λ5, 3λ5-[1,3]Diphosphinine mit Thio- und Selenophosphonsäureresten – Darstellung,Kristallstruktur, NMR-Daten und Komplexbildung mit PdII

Diphosphabenzenes. VI. New 1λ⁵, 3λ⁵-[1,3]Diphosphinines with Thio and Seleno Phosphonic Acid Groups – Preparation, Crystal Structure, NMR Data, and Coordination to Pd^II Preparation of N,N,N′,N′-tetraethyl-P-phenylethinyl phosphonothioacid diamide ( 2 ) and the corresponding phosphonoselenoacid diamide ( 3 ) are described. 2 and 3 react with 1,1,3,3-tetrakis(dimethylamino)-1λ⁵,3λ⁵-diphosphete ( 1 ) to yield 1λ⁵,3λ⁵-[1,3]diphosphinine derivatives 4 and 5 . With (bzl)₂Cl₂Pd 5 forms the coordination compound 6 . All new compounds 2–6 are characterized by their nmr and ir spectra, the structures of 4–6 are further elucidated by X-ray structural analyses.     

Mono- und Bis(difluorphosphoranyl)ethylen,n-Hexyliden-fluorphosphoran und ein 2,4-Di-n-pentyl-1λ5,3λ5-diphosphet

Mono- and Bis(difluorophosphoranyl)ethylene, n-Hexylidene-fluorophosphorane, and a 2,4-Di-n-pentyl-1λ⁵, 3λ⁵ -diphosphete Bis(diethylamino)phosphanylethylene, 1 , is converted by SF₄ into bis(diethylamino)difluorophosphoranylethylene, 2. Analogously trans-1,2-bis(diphenylphosphanyl)ethylene, 3 , is converted into trans-1,2-bis(difluorodiphenylphoranyl)ethylene, 4. 2 reacts with n-butyllithium to give n-hexylidene-bis(diethylamino)fluorophosphorane, 5. With more n-butyllithium, the main product n-hexylidene-bis(diethylamino)-n-butylphosphorane, 7 , and the by-product 2,4-di-n-pentyl-1,1,3,3-tetrakis(diethylamino)-1λ⁵, 3λ⁵ -diphosphete, 8 , are formed. With t-butyllithium 2 yields 3,3-dimethyl-butylidene-bis(diethylamino)fluorophosphorane, 6. All new compounds 1, 2, 4–8 are characterized by their nmr and ir spectra.     

o-1λ5,3λ5-Diphosphaphenylen-bis(diphenylphosphan) und seine chelatbildenden Eigenschaften

o-1λ⁵,3λ⁵-Diphosphaphenylene-bis(diphenylphosphane) and its Chelating Properties Bis(diphenylphosphanyl)acetylene and 1,1′,3,3′-tetrakis(dimethylamino)-1λ⁵,3λ⁵-diphosphete react at higher temperatures to yield the title compound 5 , which forms easily the chelate complex 6 with nickel(II) chloride.     

Synthese und NMR-Spektren von λ5-Diphospheten Die Struktur des 2,4-Diphenyl-1,1,3,3-tetrakis(diethylamino)-1λ5,3λ5-diphosphets

Synthesis and NMR Spectra of λ⁵-Diphosphets. Structure of 2,4-Diphenyl-1,1,3,3-tetrakis (diethylamino)-1λ⁵, 3λ⁵-diphosphete Preparation, properties, and n.m.r. spectra of C₂H₅PF₂[N(C₂H₅)₂]₂, CH₂?PF[N(C₂H₅)₂]₂, and the diphosphetes {RC?P[N(C₂H₅)₂]₂}₂ (R) ? H ( 5a ), CH₃ [( 5b )] are described. The λ⁵-diphosphete {HC?P(NR₂)₂}₂ (R ? CH₃) reacts with BF₃ · O(C₂H₅)₂ to give which is transformed into by n-C₄H₉Li. The crystal and molecular structure of 2,4-diphenyl-1,3,3-tetrakis(diethylamino)-1λ⁵,3λ⁵-diphosphete 2 are reported and discussed.     

Röntgenstrukturanalyse des 1,3-Bis(diethylamino)-1,3-dibenzyl-2,4-diphenyl-1λ5, 3λ5-diphosphets

X-Ray Crystal Structure Determination of 1,3-Bis(diethylamino)-1,3-dibenzyl-2,4-diphenyl-1λ⁵, 3λ⁵-diphosphete Benzylidene-diethylamino-benzylfuorophosphorane, 1 , reacts with lithium bis(trimethylsilyl)amide to give the title compounds 2 and 1-diethylamino-2,3-diphenylphosphirane, 3 . Only one of the stereoisomers of 2 is formed in which the two benzyl groups are located on the same side of the planar four-membered ring. 2 crystallizes in the monoclinic space group P2₁/n.     

Eine cyclische Methylendiphosphinsäure: 1,3‐Dihydroxy‐1,3‐dioxo‐1,2,3,4‐tetrahydro‐1λ5,3λ5‐[1,3]diphosphinin

A Cyclic Methylenediphosphinic Acid: 1,3‐Dihydroxy‐1,3‐dioxo‐1,2,3,4‐tetrahydro‐1λ⁵,3λ⁵‐[1,3]diphosphinine Strong acids protonate 1,3‐bis(dimethylamino)‐1λ⁵,3λ⁵‐[1,3]diphosphinine ( 5 ) to give the corresponding cation. The protonation is followed by hydrolytic cleavage of the dimethylamino groups resulting in the formation of the cyclic methylenediphosphinic acid ( 6 ).     

Acyl- und Alkylidenphosphane. XXII [1]. Synthese und Struktur des 1, 3-Dimethyl-2,2,4,4-tetrakis-(trimethylsilylsulfano)-1,3-diphosphetans

Acyl- and Alkylidenephosphines. XXII. Synthesis and Structure of 1, 3-Dimethyl-2,2,4,4-tetrakis(trimethylsilylsulfano)-1,3-diphosphetane At ?30°C methylbis(trimethylsilyl)phosphine reacts with carbon disulfide to give a red adduct first which rearranges to [bis(trimethylsilylsulfano)methylidene]methylphosphine 1a . In contrast to the thermally stable phenyl derivative 1b [2], this compound with its insufficiently shielded P?C group dimerizes fast with increasing temperature. 1,3-Dimethyl-2,2,4,4-tetrakis(trimethylsilylsulfano)-1,3-diphosphetane 2a formed by this reaction, crystallizes in the triclinic space group P1 with following dimensions of the unit cell, determined at a temperature of measurement of ?80 ± 3°C: a = 1024.7(3); b = 1360.2(5); c = 1326.3(6)pm; α = 117.85(4); ß = 111.05(3); γ = 72.09(3)°; Z = 2. Due to ring folding at the P1? P2 axis of 149.1°, the molecule shows pseudosymmetry C_s. Characteristic averaged bond lengths and angles obtained at an R_w-value of 0.030, are: P? C(endocyclic) 188 and 191; P? CH₃ 184; C? S 183; S? Si 216 pm; C? P? CH₃ 105; P? C? S 113; S? C? S 114; C? S? Si 108; P? C? P 90 and C? P? C 86°.     

peri-Naphthylenediamines

4,5,4′,5′-Tetrakis(dimethylamino)-1,1′-binaphthalene, unknown previously, was obtained in ∼20% yield by the oxidation of 1,8-bis(dimethylamino)naphthalene with Tl(OAc)₃ or Pb(OAc)₄ at low temperatures. Treatment of the reaction product with excess Li and then with O₂ gave, depending on the reaction temperature, perylene or 4,4′-bis(dimethylamino)-1,1′-binaphthalene in good yields, instead of expected 3,4,9,10-tetrakis(dimethyl-amino)perylene. For Part 23, see Ref. 1. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 93–98, January, 1998.     

Iron carbonyl complexes of 2,3,5,6-tetrakis(methylene)-7-oxabicyclo[2.2.1]heptane. Crystal and molecular structure of (C10H10O)Fe(CO)3 and (C9H10CO)Fe2(CO)6

The reaction of 2,3,5,6-tetrakis(methylene)-7-oxabicyclo[2.2.1]heptane (I) with iron carbonyls in various solvents yields the (η⁴-1,3-diene)Fe(CO)₃ isomers (II: exo; III: endo) and the bimetallic isomers bis[(η⁴-1,3-diene)Fe(CO)₃] (IV: bis(exo); V: endo,exo). In weakly coordinating solvents, a parallel rearrangement of I occurs through CO bond cleavage of the allylic ether by Fe₂(CO)₉ yielding an unsaturated ketone (VI) bonded to two Fe(CO)₃ groups through a trimethylenemethane and a 1,3-diene system, respectively. The geometries of III and VI have been ascertained by X-ray crystal structure determinations.     

Structure determination of a bis[4-(di-n-butylamino)phenyl](pyridin-3-yl)borane tetramer highlighting a unique geometric conformation of the core 16-membered ring

The tetramer of bis(4-di-n-butylaminophenyl)(pyridin-3-yl)borane [systematic name: 2λ⁴,4λ⁴,6λ⁴,8λ⁴-tetrabora-1,3,5,7(1,3)-tetrapyridinacyclooctaphane-1¹,3¹,5¹,7¹-tetrakis(ylium)], C₁₃₂H₁₉₂B₄N₁₂, was synthesized unexpectedly and crystallized. Its structure contains an unusual 16-membered ring core made up of four (pyridin-3-yl)borane groups. The ring adopts a conformation with pseudo-S₄ symmetry that is very different from the two other reported examples of this ring system. Density functional theory (DFT) computations indicate that the stability of the three reported ring conformations is dependent on the substituents on the B atoms, and that the pseudo-S₄ geometry observed in the bis(4-dibutylaminophenyl)(pyridin-3-yl)borane tetramer becomes significantly more stable when phenyl or 2,6-dimethylphenyl groups are attached to the boron centers.     

Eine neue Synthese von Tetrachlordiphosphan sowie Untersuchungen zur 1,2-Addition an Cycloalkene

A New Synthesis of Tetrachlorodiphosphane and Investigations Concerning the 1,2-Addition to Cycloalkenes . The phosphorus subhalide P₂Cl₄ has been synthesized by co-condensation of PCl₃ and Cu vapour in 14% yield. The ³¹P-NMR chemical shift of P₂Cl₄ has the value of δ=155. P₂Cl₄ decomposes during several hours at 0°C in a N₂ atmosphere by a disproportionation process to yield PCl₃ and a yellow polymeric compound of the approximately composition (PCl)_x. P₂Cl₄ is flammable in air to give POCl₃ and (PCl)_x. Investigations regarding the addition of P₂Cl₄ to cyclooctyne, cyclohexene, and cyclohexa-1,4-diene has been carried out. Surprisingly, cyclooctyne does not react with P₂Cl₄ but cyclohexene as well as cyclohexa-1,4-diene undergo 1,2-addition to yield the trans-1,2-bis(dichlorophosphino) substituted carbonhydrides. By derivatization with Me₃Si—NMe₂ the corresponding trans-1,2-bis[bis(dimethylamino)phosphino] compounds are synthesized.