Dérivés Alléniques du Phosphore. Influence de l'État de Coordination du Phosphore et de la Nature des Radicaux Liés au Phosphore sur les Signes de J(PH)

Les signes des constantes de couplage phosphore-proton dans les derives alleniques du phosphore ont ete determines soit par analyse des spectres de type AB2X, soit par Double Resonance, et les signes absolus probables ont ete obtenus en supposant que 3J(PH) est toujours positif. Dans les oxydes de phosphines alleniques, les signes sont les suivants: 2J(PH) +, 3J(PH) +, 4J(PH) −, 5J(PH) + et 4J(PH) depend principalement des effets inducteurs des radicaux lies au phosphore. Dans les phosphines alleniques, les signes sont: 2J(PH) +, 3J(PH) +, 4J(PH) − et + et 4J(PH) depend a la fois des effets inducteurs et de resonance des radicaux lies au phosphore: ce couplage, normalement negatif, deviant positif lorsque le phosphore porte des substituants donneurs par effet de resonance. Ces resultats sont interpretes par l'existence d'une liaison pπdπ dans les phosphines. The signs of the phosphorus-proton coupling constants in various allenic organophosphorus compounds have been determined by either analysis of the AB2X spectra or double resonance. Probable absolute signs have been obtained by taking 3J(PH) as positive. In allenic phosphine oxides, the following signs are obtained: 2J(PH) +ve, 3J(PH) +ve, 4J(PH) −ve, 5J(PH) +ve and the 4J(PH) coupling constant varies mostly with the inductive effect of the substituents bound to the phosphorus atom. In allenic phosphines, these sings are: 2J(PH) +ve, 3J(PH) +ve, 4J(PH) −ve and +ve and the 4J(PH) coupling constant varies with both the inductive and resonance effects to the substituents. This coupling constant is negative except when the phosphorus atom is bound to groups which are electron-donating by resonance effects. These results are discussed in relation to the pπdπ bonding in phosphine.

[1]  J. Labarre,et al.  N° 38 — Moments dipolaires des molécules des types P(XYZ) ET OP(XYZ) : contribution à l'étude de la nature de la liaison (P.O) , 1968 .

[2]  Kensuke Takahashi,et al.  Nuclear Magnetic Resonance Spectra of Organophosphorus Compounds. II. The Relative Signs of the Coupling Constants between Phosphorus and Proton , 1967 .

[3]  J. Lancaster.  Use of double quantum spectra in the analysis of vinyl-phosphorus proton NMR spectra , 1967 .

[4]  Kensuke Takahashi,et al.  Nuclear Magnetic Resonance Spectra of Organophosphorus Compounds. I. Long-range Coupling between Phosphorus and Proton through Four Bonds , 1966 .

[5]  D. Grant,et al.  Interpretation of NMR Spectra. I. A2BXx and A2BKk Spectra , 1966 .

[6]  E. Cherbuliez,et al.  276. Recherches sur la formation et la transformation des esters LXVIII [1]: Sur la réaction entre dichlorophénylphosphine et hexyne‐l‐ol‐3 , 1966 .

[7]  E. Duval,et al.  The absolute signs of the 31P-1H coupling constants in the nuclear magnetic resonance spectra of triethylphosphite, triethylphosphate and triethyl (0, 0, 0) thiophosphate , 1966 .

[8]  A. Cowley,et al.  A Proton Magnetic Resonance Study of Some Dialkylaminophosphorus Derivatives , 1965 .

[9]  E. Cherbuliez,et al.  Recherches sur la formation et la transformation des esters LVII. Acides ou chlorures d'acides de PIII et alcools α‐acétyléniques: estérification sans ou avec réarrangement , 1965 .

[10]  H. Bernstein,et al.  ADDENDUM: A SIMPLIFIED PROCEDURE FOR THE ANALYSIS OF COMPLEX NUCLEAR MAGNETIC RESONANCE SPECTRA: I. THE PRINCIPLES OF SUB-SPECTRAL ANALYSIS , 1965 .

[11]  J. F. Nixon,et al.  Phosphorus-31 nuclear magnetic resonance studies of phosphorus—fluorine compounds , 1964 .

[12]  R. Harris,et al.  NUCLEAR MAGNETIC RESONANCE STUDIES OF COMPOUNDS RELATED TO TETRAMETHYLDIPHOSPHINE DISULPHIDE , 1964 .

[13]  R. C. Ferguson.  Proton Magnetic Resonance Spectrum of 4-Chloro-1,2-butadiene , 1964 .

[14]  J. B. Hendrickson,et al.  Correlation of proton chemical shift and 31P-H spin-spin coupling constants for organophosphorus derivatives , 1964 .

[15]  W. A. Anderson,et al.  ASSIGNMENT OF NMR SPECTRA WITH THE AID OF DOUBLE-QUANTUM TRANSITIONS , 1963 .

[16]  G. L. Juvinall,et al.  The relative signs of phosphorus-proton nuclear magnetic resonance coupling constants. , 1963 .

[17]  E. Wagner.  Calculated Bond Characters in Phosphoryl Compounds , 1963 .

[18]  John D. Roberts,et al.  Long-Range Nuclear Spin-Spin Coupling. Allenic and Polyacetylenic Systems , 1962 .

[19]  A. Boisselle,et al.  Acetylene-Allene Rearrangements. Reactions of Trivalent Phosphorus Chlorides with α-Acetylenic Alcohols and Glycols , 1962 .

[20]  D. Elleman,et al.  DOUBLE RESONANCE STUDY OF THE N.M.R. SPECTRUM OF 1-CHLOROBUTADIENE-1,2 AND THE DETERMINATION OF THE RELATIVE SIGNS OF THE COUPLING CONSTANTS , 1962 .

[21]  J. D. Guthrie,et al.  Derivatives of Unsaturated Phosphonic Acids , 1961 .

[22]  R. Freeman,et al.  Determination of the relative signs of proton spin coupling constants by double irradiation , 1961 .