Gernot Heckmann

Extremely large one‐bond 31P13C and two‐bond 31P18O isotope shifts in [(H3C)2CH]3SiOCP, a new representative of λ3‐phosphaalkynes, and isotope shifts of several derivatives and some λ3‐phosphaalkenes

The structure of the heteroatom‐substituted λ3‐phosphaalkyne [(H3C)2CH]3SiOCP (1) was derived from the 31P, 13C, 29Si and 17O NMR spectra. The phosphorus atom of the non‐isotope‐enriched compound exhibits an extremely negative 31P13C one‐bond and 31P18O two‐bond isotope shift of −0.209 and −0.094 ppm, respectively. The 31P{1H} NMR spectrum shows all carbon, silicon and oxygen satellite signals of the [mono‐13C]‐, [mono‐29Si]‐ and [mono‐18O]‐ as well as the [bis‐13C, 29Si]‐ and [bis‐13C, 13C]isotopomers; even over five bonds a 31P 13C isotope effect can also be observed. Additivity of the corresponding isotope effects has been confirmed. The coupling constant 1J(31P,13C) is unexpectedly large, 91.9 Hz. 31P13C one‐bond isotope shifts of other λ3‐phosphaalkynes and λ3‐phosphaalkenes are presented and discussed. Copyright

DIE REAKTION VON 1,1,3,3-TETRAKIS-(DIMETHYLAMINO)-DIPHOSPHET MIT SCHWEFELKOHLENSTOFF, I

Abstract 1,1,3,3-Tetrakis(dimethylamino)-diphosphete, 1, reacts with CS2 to give 1,1,3,3-tetrakis(dimethylamino)-1-phospha-3-phosphonium-2-dithio-carboxylato-cyclobutene-1, 2. The new compound is characterized by its nmr-, mass-, and ir-spectra. 1,1,3,3-Tetrakis(dimethylamino)-diphosphet, 1, reagiert mit CS2 zu 1,1,3,3-Tetrakis(dimethylamino)-1-phospha-3-phosphonium-2-dithio-carboxylato-cyclobuten-1, 2. Die neue Verbindung ist durch ihre NMR-, Massen- und IR-Spektren charakterisiert.

DIE REAKTION VON 1,1,3,3-TETRAKIS(DIMETHYLAMINO)-1Λ5,3Λ5-DIPHOSPHET MIT ACETONITRIL

Abstract Reaction of 1,1,3,3-tetrakis(dimethylamino)-1Λ5,3Λ5-diphosphete 1 with acetonitrile yields 3,3,5,5-tetrakis(dimethylamino)-3,5-diphospha-hexa-2,4-dienenitrile, 2. Properties, NMR spectra and the results of an X-ray structural analysis are reported. Die Umsetzung von 1,1,3,3-Tetrakis(dimethylamino)-1Λ5,3Λ5-diphosphet 1 mit Acetonitril liefert 3,3,5,5-Tetrakis(dimethyl-amino)-3,5-diphospha-hexa-2,4-diennitril, 2. Eigenschaften, NMR-Spektren und die Ergebnisse einer Rontgenstrukturanalyse werden mitgeteilt.

REACTION OF 1,1,3,3-TETRAKIS(DIMETHYLAMINO)-1λ5,3λ5-DIPHOSPHETE, 1, WITH CARBONDISULFIDE II. DIHYDRO-λ5-PHOSPHETES; NMR ISOTOPE EFFECTS

Abstract 1,1,3,3-Tetrakis(dimethylamino)-1-phospha-3-phosphonium-2-dithio-carboxylato-cyclobutene-1, 2,1 is thermally unstable. By heating it is converted quantitatively into [1,1-bis(dimethylamino)-3-thioxo-3,4-dihydro-1λ5-phosphete-2-yl]-phosphonothioic bis(dimethylamide), 3. Reaction of the 2,4-dimethylderivative of the title compound 1, i.e. 4, with CS2 yields [1,1-bis(dimethylamino)-2,4-dimethyl-3-thioxo-2,3-dihydro-1λ5-phosphete-2-yl]-phosphonothioic bis(dimethylamide) 7. The new compounds are characterized by their properties and their nmr, it and mass spectra. Isotope effects on δ31P of 7 are described. The results of the X-ray structural analyses of 3 and 7 are reported and discussed.

o-λ5-[1,3]-Diphosphaphenylen-bis(diphenylphosphanoxid) und sein palladium(ii)-komplex

Abstract 4,5-Bis(diphenylphosphanoyl)-octa- N -methyl-1λ 5 ,3λ 5 -[1,3]-diphosphinin-1,1′3,3′-tetraamin ( o -λ 5 -[1,3]-diphosphaphenylene-bis(diphenyl-phosphanoxide)), 2 , is formed from compound 1 by aeration. Compound 2 acts as a chelating ligand owing to the anionic nature of two ylidic carbon atoms in the reaction with (benzonitrile) 2 PdCl 2 to form complex 3 . Compound 2 is characterized by its NMR and IR spectra, and compound 3 by the results of an X-ray structural analysis.

REAKTIONEN DES 1,1,3,3-TETRAKIS(DIMETHYLAMINO)-1λ5,3λ5- DIPHOSPHETS MIT CARBONYLAKTIVEN VERBINDUNGEN

Abstract Reaction of 1,l,3,3-tetrakis(dimethylamino)-lλ5,3λ5-diphosphete (1) with benzaldehyde yields [(2-phe-nyl-l-ethenyl)- bis(dimethylamino)phosphoranylidene]methylphosphonicbis(dimethylamide) (2), while 1 reacts with phenylisocyanate to give the heterocyclic compound 3, i.e., l-phenyl-2,2,4,4-tetrakis(dimethylamino)-6-oxo-l,2λ5,4λ5-azadiphosphorine. 2 and 3 are characterized by their nmr, mass, and i.r. spectra. In 3, the signs of the coupling constants 1J(PC2) and 3J(PC2) are found to be opposite. Mechanisms for the formation of 2 and 3 are discussed. 1,1,3,3-Tetrakis(dimethylamino)-lλ5,3λ5-diphosphet (1) reagiert mit Benzaldehyd zu [(2-Phenyl-1-ethenyl)-l-bis(dimethylamino)phosphoranyliden]methylphosphonsaurebis(dimethylamid) (2). Wahrend mit Phenylisocyanat die heterocyclische Verbindung 3. d.i. I-Phenyl-2,2,4,4-tetrakis-(dimethylamino)-6-oxo-l,2λ5,4λ5-azadiphosphorin gebildet wird. 2 und 3 sind durch ihre NMR-, Mas-sen- und IR-Spektren charakterisiert. In 3 haben die Kopplungskonstanten 1J(PC2) u...

1,2λ5,4λ5-AZADIPHOSPHORINE (2λ5,4λ5-DIPHOSPHAPYRIDINE)

Abstract 1.1,3.3-Tetrakis(dimethylamino)-diphosphete, 4. reacts with henzonitrile and p-trifluoromethylbenzo-nitrile to give 2.2.4.J-tetrakis(dimethylamino)-h-phenyl-1.2λ5.4λ5-azadiphosphorine. 5. and 2.2.4.4-tetrakis(dimethylamino)-6-(4-trifluoromethylphenyl)-1.2λ.5 4λ5-azadiphosphorine. 6. The new compounds are characterized by their nmr-. mass- and ir-spectra. In addition, the results of an X-ray structural analysis of 6 are described. 1.1,3.3-Tetrakis(dimethylamino)-diphosphet 4 reagiert mit Benzonitril und p-Trifluormethylhcnzo-nitril zu 2.2.4.4-Tetrakis(dimethylamino)-6-phenyl-1.2λ5.5λ5-azadiphosphorin 5 und 2.2.4.4.-Tetrakis-(dimethylamino)-6-(4-trifluormethylphenyI)-1.2λ5.5λ5-azadiphosphorin 6. Die neuen Verbindungen sind durch ihre NMR-. Massen- und IR-Spektren charakterisiert. Fur 6 werden die Ergehnisse einer Riint-genstrukturanalyse beschrieben.

REAKTIONEN DES 1,1′,3,3′-TETRAKIS(DIMETHYLAMINO)-1λ5,3Δ5-DIPHOSPHETS MIT ALKOHOLEN. ALK(PHEN)OXYCARBODIPHOSPHORANE

Abstract Alcoholysis of 1,1′,3,3′-tetrakis(dimethylamino)-1λ5,3Δ5-diphosphete 1 with methanol, ethanol, n-propanol, n-butanol, and phenol yields the alk(phen)oxy substituted carbodiphosphoranes 4–8. The new compounds are characterized by their nmr and mass spectra. Contrarily, alcoholysis of 1 with t-butanol or 1,4-butanediol forms compound 2, which is also the primary product of hydrolysis of 1.

31P-KERNRESONANZUNTERSUCHUNGEN VON P4S9 UND P4S10

Abstract The preparation of P4P9 from P4S3 and sulfur in decalin is described. The 31P nmr spectra of P4S9 and P4S10 are presented and discussed. Die Darstellung von P4S3 aus P4S3 und Schwefel in Dekalin wird beschrieben. Die 31P-NMR-Spektren von P4S9 und P4S10 sind angegeben und interpretiert.

Synthese und Struktur von bis[η5-(cyclopropyl-cyclopropyliden-methyl)-cylopentadienyl]bis(tetrahydrofuran-O)calcium

Abstract The reaction of bis(tetrahydrofuran- O )calcium bis[bis(trimethylsilyl)amide] 1 in tetrahydrofuran with two equivalents of 6,6-di( cyclo -propyl)fulvene at 60°C yields within 150 h bis[ η 5 -(cyclopropyl-cyclopropyliden-methyl)cyclopentadienyl]bis(tetrahydrofuran- O )calcium 2 . As an intermediate the heteroleptic bis(tetrahydrofuran- O )calcium bis(trimethylsilyl)amide [ η 5 -(cyclopropylcyclopropylidenmethyl)cyclopentadienide] 3 is detected by 1 H and 13 C{ 1 H} NMR spectroscopy. In solution an equilibrium involving these three derivatives exists. 2 crystallizes at −20°C from tetrahydrofuran as colorless cuboids (monoclinic, C 2/ c ; a = 1175,2(1); b = 1182,1(1); c = 2040,0(3) pm; β = 101,015(9)°; Z = 4; wR 2 = 0,1410). The metal center is surrounded distorted tetrahedrally by the four ligands. The cyclopentadienyl group and the propylidene fragment are oriented coplanar.