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  • 11
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 118 (1985), S. 3227-3240 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: λ5-Di- and -Triazaphospholines - Synthesis, Isomerization, and DecompositionThe reaction of amino[(trimethylsilyl)methylene]thioxophosphorane 1 with diazoalkanes leads to Δ1-diazaphospholines 3, 7, 11, and 12. These sensitive compounds are stabilized by 1,3-migration of a trimethylsilyl group, where 3 and 7 end in the Δ2-diazaphospholines 4 and 8 and 11 and 12 decompose by [1 + 4]cycloreversion to give the azines 14 and 15 as well as aminothioxophosphane intermediate 13. 13 could be trapped by reaction with diazoalkanes as aminomethylenethioxophosphoranes (18 and 19). The corresponding phosphane system 20 and 21 is available by reduction of 18 and 19, respectively, with triphenylphosphane. tert-Butyl azide (22) and 1 form triazaphospholine 23, which isomerizes thermally by silyl migration to give 24. Photochemically induced elimination of N2 leads to the λ5-azaphosphiridine 25; this system is also accessible by reaction of aminoiminothioxophosphorane 26 with diazomethane. In contrast, thermal reaction of trimethylsilyl azide (30) and 1 results in a λ5-thiaphosphirane 31. Compounds of this type (31, 32) can also be synthesized by [1 + 2]cycloaddition of sulfur and the corresponding iminomethylenephosphorane. - The X-ray structure analysis of the Δ2-diazaphospholine 5 is described, NMR data and decomposition of di- and triazaphospholines are discussed.
    Notes: Amino[(trimethylsilyl)methylen]thioxophosphoran 1 reagiert mit Diazoalkanen zu den Δ1-Diazaphospholenen 3, 7, 11 und 12. Diese stabilisieren sich unter 1,3-Trimethylsilyl-Verschiebung zu den Δ2-Diazaphospholenen 4 und 8 bzw. zerfallen unter [1 + 4]-Cycloreversion zu Azin (14 und 15) und dem Aminothioxophosphan 13. 13 konnte durch Reaktion mit Diazoalkan als Aminomethylenthioxophosphoran (18 und 19) abgefangen werden. Durch Entschwefelung von 18 bzw. 19 mittels Triphenylphosphan ist das entsprechende Phosphan-System 20 bzw. 21 zugänglich. tert-Butylazid (22) reagiert mit 1 zum Triazaphospholen 23, das thermisch unter Trimethylsilyl-Wanderung zu 24 isomerisiert und photochemisch unter N2-Eliminierung das λ5-Phosphiridin 25 liefert, ein Verbindungssystem, das ebenfalls durch Umsetzung eines Aminoiminothioxophosphorans (26) mit Diazomethan zugänglich ist. Bei der thermischen Reaktion von 1 und Trimethylsilylazid (30) wird hingegen das λ5-Thiaphosphiran 31 erhalten. Verbindungen dieses Typs (31, 32) sind auch durch Schwefelung der entsprechenden Iminomethylenphosphorane zugänglich. - Die Röntgenstrukturanalyse des durch partielle Hydrolyse von 4 erhaltenen Δ2-Diazaphospholens 5 wird angegeben, und die NMR-Daten sowie der Zerfall der Di- und Triazaphospholene werden diskutiert.
    Additional Material: 5 Tab.
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  • 12
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 121 (1988), S. 565-568 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: On the Reaction of tert-Butyl(tert-butylimino)phosphane with tert-Butyl(tert-butylimino)boraneContrary to the [2 + 2] cycloaddition reaction of aminoiminophosphanes with iminoboranes, the title compounds react to yield the heterocyclic products 7 and 9, the structures of which were determined by means of spectroscopic methods and, in the case of 9, additionally by X-ray structural analysis. Further investigations on the reaction mechanism suggest that the first step of the reaction sequence is an oxidative [2 + 1] cycloaddition of the iminophosphane 3 to 2.
    Additional Material: 1 Ill.
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  • 13
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 124 (1991), S. 1973-1976 
    ISSN: 0009-2940
    Keywords: 2-Phosphonioallene ligands ; Metallobis(methylene)phosphoranes ; Nickel complexes ; Platinum complexes ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Synthesis and Structure of 2-Phosphonioallene ComplexesThe reaction of the chlorobis(methylene)phosphorane 1 with reactive olefin complexes of nickel and platinium affords the 2-phosphonioallene complexes 4b and 6a,b. The structure of this new class of three-electron donor ligands, involving a lowcoordinated phosphorus (V) cation, has been elucidated by NMR spectroscopy and a single-crystal X-ray study of 6a. The reaction proceeds via a metallobis(methylene)phosphorane intermediate, which could be isolated in the case of the (Et3P)2Pt complex 3a.
    Additional Material: 1 Ill.
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  • 14
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 125 (1992), S. 321-330 
    ISSN: 0009-2940
    Keywords: Phosphanes, (Z)-amino(imino)- ; 1,3,5-Triaza-2,4-diphospha-1,4-pentadienes, transition metal complexes of, dynamic behavior of ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: On the Knowledge of the 1,3,5-Triaza-2,4-diphospha-1,4-pentadienesHerrn Professor Heinrich Puff zum 70. Geburtstag gewidmetNucleophilic substitution reactions of the chloro(arylimino)-phosphane 1 yield the NH-functional amino(imino)phosphanes Mes*NPNHR (R = Mes, Ad, CPh3) 2d - f. Upon further reaction with 1 they are converted into the 1,3,5-triaza-2,4-diphospha-1,4-pentadienes Mes*NPN(R)PNMes* (R = Mes, Ad) 4d, e and Mes*NPN(Mes*)PNCPh3 5. According to crystal structure determinations all compounds 4a, d, e, 5 exhibit S conformation in the solid state. In addition to the “exo-endo” arrangement of the substituents (4a, 5) in the case of 4d, e the “endo-endo” conformation is observed for the first time. In solution, 4d, e and 5 are subject to dynamic rearrangements, whose mechanism is proven by NMR studies of partially 15N-enriched samples. The reaction of 4a with NorM(CO)4 (M = Cr, Mo) or Ni(CO)4 yields the metallaazadiphosphetidine complexes 6a - c Mes*NPN(tBu)PNMes*M(CO)n [M(CO)n = Cr(CO)4, Mo(CO)4, Ni(CO)2]. The crystal structure of 6a (“exo-endo-W”) is described.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
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  • 15
    ISSN: 0009-2940
    Keywords: 1,3-Diaza-2-phosphaallyllithium ; Calculations, ab initio ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Monomer and Dimer 1,3-Diaza-2-phosphaallyllithium Complexes: Structures and Ambident Reactivity*Metallation of the NH-functional amino(imino)phosphanes Mes*NPNHR (R = CPh3, Ad, tBu) 1a-c yields the 1,3-diaza-2-phosphaallyllithium compounds 2a-c. The crystal structure shows an ether-stabilized monomer of 2a and a solvent-free dimer with an eight-membered ring in the case of 2b, c. The reaction of 2b with chlorodiphenylphosphane yields, dependent on the reaction conditions, (phosphanylamino)iminophosphane 3 or bis(imino)phosphanylphosphorane 4. The structural and reactivity is discussed on the basis of ab initio calculations.
    Additional Material: 4 Ill.
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  • 16
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 125 (1992), S. 2635-2640 
    ISSN: 0009-2940
    Keywords: Alkyl(arylimino)phosphanes ; [4 + 1] Selfaddition reactions ; [n + 1] Cycloaddition reactions ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Reversible [4 + 1] Selfaddition of Alkyl(arylimino)phosphanes and Regioselective Cycloaddition to (E)- and (Z)-AzobenzeneDehydrohalogenation of the amino(chloro)phosphanes RP(Cl)N(H)Aryl (1; R=Me, Et; Aryl = 2,4,6-Tri-tert-butylphenyl) affords the corresponding iminophosphanes RP= NAryl (2) which undergo a reversible [4 + 1] selfaddition with participation of the aryl substituent to form 3,3a-Dihydro-2H-1,2,3λ5-benzoazadiphospholes 3. The regioselective cycloaddition of 2b towards (E)- and (Z)-azobenzene (4a and b) has been demonstrated in the formation of two different phospholes 6 and 8 which are formed by a [2 + 1] and [4 + 1] cycloaddition reaction of the iminophosphane 2b. The structure of the fiveymembered ring systems 3, 6 and 8 has been elucidated by NMR spectroscopy and single-crystal X-ray studies of 3b and 6.
    Additional Material: 2 Ill.
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  • 17
    ISSN: 0009-2940
    Keywords: Methylenephosphanyl complexes ; Phosphenium complexes ; Phosphavinylidene complexes ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Methylenephosphanyl Complexes of Chromium, Molybdenum, Tungsten, Iron and Nickel - Synthesis and ReactivityHerrn Professor Heinrich Nöth zum 65. Geburtstag gewidmet.The reaction of the functionalized P/C double bond systems X - P=C(R)SiMe3 [R=SiMe3 and X=Cl (1a), Cp* (5a) or R=Ph and X=Br (1b), Cp* (5b)] with alkali carbonylmetallates or carbonyl complexes of group 6, 8, and 10 metals leads to the formation of the transition metal-substituted phosphaalkenes [{M} - P=C(R)SiMe3 3a - j and 4a - i], in which the P - C fragment acts as a one-electron donor. Depending on the nucleophilicity of the transition metal anion used, but also on the methylene carbon substituents [1a: (SiMe3)2: 1b: (Ph)1-SiMe3], a different stability of the (methylenephosphanyl)1-metal complexes is observed, which results in a broad spectrum of reactivities. As demonstrated by the reactions of the (methylenephosphanyl)metal complexes with sulfonic acid derivatives (10a - c), diverse transition metal complexes (11a - c), as well as chalcogenes (14a - c, 15), a change in the reactivity is observed, indicating a transition from an olefinic to a carbenic character of the methylenephosphane. In comparison to the phenyl-substituted derivatives 4a - i the bis(trimethyl)1-substituted species 3a - j exhibit an increased reactivity. This is reflected in the easy decarbonylation of 3a - d to the phosphavinylidene complexes 12a - d.
    Additional Material: 3 Ill.
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  • 18
    ISSN: 0009-2940
    Keywords: 1,3,5-Triaza-2,4-diphospha-1,4-Pentadienes, dynamic behavior ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Synthesis, Molecular Structure, and Dynamic Behaviour of 1,3,5-Triaza-2,4-diphospha-1,4-pentadienesChloro(arylimino)phosphane (1) reacts with the 1,3-diaza-2-phosphaallylic system 3 to form 1,3,5-triaza-2,4-diphospha-1,4-pentadienes Ar-N=P-N(R)-P=N-Ar (Ar = 2,4,6-tBu3-C6H2; R = tBu, 2,4,6-iPrc3C6H2) (4a-c). the molecular structure of 4a (“Exo-endo-S conformation”) as well as the dynamic behaviour of the compounds in solution are discussed. the observed temperature dependance of the NMR spectra of 4c was interpreted as a sigmatropic 1,3-rearrangement followed by a P-N rotation.
    Additional Material: 1 Ill.
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  • 19
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 127 (1994), S. 313-319 
    ISSN: 0009-2940
    Keywords: Phosphirene imines ; 1,2-Diphosphete diimines ; Isomerization ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Investigations of the System Phosphirene Imine/Iminophosphane - Insertion and Isomerization ReactionsTreatment of the iminophosphanes R1P=NR2 1 [R2 = tBu, R1 = Et3C (a); R2 = Aryl, R1 = Et (b), Me (c)] with 1,4-diphenyl-butadiyne (2) leads to the phosphirene imines R1-(R2N=)P̌(Ph)=CCCPh 3a-c and [R1(R2N=)P̌(Ph)=CC]2 4a-c. Further reaction with 1a, c gives the 1,2-diphosphetes R1(R2N=)PP(R1)(=NR2)C(Ph)=CCCPh 5a, b, which isomerize in the case of R1 = Me into the triphosphabicyclo[3.2.0]-hepta-1,6-diene 7. In the reaction of the phosphirene imines R1(ArylN=)P̌(R2)=C(R2) 3 [R1 = Me, R2 = Ph (d); R1 = Et, R2 = COOMe (e)] with the iminophosphanes 1b, d the initially formed diphosphetes 9a, b isomerize to the 1,2-diazaphosphole Cl(Mes*N=)PN(Mes*)P(Me)C(Ph)=C(Ph) 10 or the dioxadiphosphabicyclooctadiene C=C(OMe)OP(=N-Mes*)(Et)C=C(OMe)OP(=NMes*)(Et) 12 depending on the substituents. A reaction of the phosphirene imine 3d with dimethylamino-borane furnishes the vinylphosphane. Ph(H)C=C(Ph)P(Et)N(H)Mes* (14) by ring opening. The compounds 7, 10, 12 have been characterized by X-ray structure analyses.
    Additional Material: 3 Ill.
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  • 20
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 116 (1983), S. 1678-1681 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: [2 + 2]-Cycloaddition Products from lminoborane and IminophosphaneThe iminoborane Bu—B=N—tBu (1a) and the iminophosphanes R2N—P=N—R′ (2a, b) undergo a cyclisation to the corresponding 1,3,2,4-diazaphosphaboretidines (3a, b).
    Additional Material: 5 Tab.
    Type of Medium: Electronic Resource
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