Crystal structure of dimethylaminodifluorophosphine, (CH3)2NPF2

Abstract

Dimethylaminodifluorophosphine, (CH3)zNPFz (mp -W0), crystallizes with four formula units in an orthorhombic cell with a = 10.808 (12) A, b = 7.601 ( 7 ) A, and c = 6.259 (6) b a t -110'. A total of 458 photographically recorded and visually evaluated X-ray data were used to determine the structure, which has been refined to R = 0.069. A space group ambiguity was resolved in favor of Pnma following least-squares refinement in both Pnma and PnZia and consideration of the effect of a slight scaling error in the weakest observed reflections. The molecule possesses mirror symmetry with the planar P-K-C skeletofi lying in a crystallographic mirror plane. Bond lengths and standard deviations are P-N = 1.628 ( 5 ) , P-F = 1.610 (4), and C-N = 1.460 (9) and 1.485 (8) b.

(2-Fluoro-1,3-dimethyl-1,3,2-diazaphospholidine)tetracarbonyliron(0)

“…These data clearly suggest a p~---d,~ interaction between the N lone-pair electrons and the P atom. Similar bond distances have been observed in the compounds (CH3)~NPF2 (Morris & Nordman, 1969), P-N = 1.628 (5) A, and NHEPF 2 (Brittain, Smith, Lee, Cohn & Schwendeman, 1971) whose microwave determination gave P--N = 1.650 (4) A. The P-N bond distances determined in this study are longer than that reported for (CH3)ENPFEB4H8 (La Prade & Nordman, 1969), P--N = 1.585 (6) A.…”

The crystal and molecular structures of 2-thiono-2-N-(diisopropylamino)-1,3,2-dithiophosphorinane and of 2-thiono-2-aziridino-1,3,2-dithiaphosphorinane

“…Such planarity is common in amino-phosphorus compounds in which an acyclic amino group is in ct position to a three- (Morris & Nordman, 1969;Brittain, Smith, Lee, Cohn & Schwendeman, 1971;Forti, Damiani & Favero, 1973) or four-coordinate (Camerman & Camerman, 1973; The plane of the C-N bonds bisects the S(1)-P-S(3) angle and N-C(9) eclipses the P=S double bond. This stereochemistry around the P--N bond seems to be quite general in three-and four-coordinated P compounds and can explain the equatorial orientation of the P-N bond.…”

Aminophosphanes with bulky amino groups: Molecular structure, coupling constants 1J(31P, 15N) and 2J(31P, 29Si), and isotope‐induced chemical shifts 1Δ14/15N(31P)

“…were studied by 1 H, 13 C, 15 N, 29 Si, and 31 29 Si) were determined. Low temperature NMR spectra were measured for derivatives for which rotation about the P N bond at room temperature is fast, showing the presence of two rotamers at low temperature.…”

“…Low temperature NMR spectra were measured for derivatives for which rotation about the P N bond at room temperature is fast, showing the presence of two rotamers at low temperature. The respective conformation of these rotamers could be assigned by 13 C, 15 N, and 31 P NMR spectroscopy. Isotope-induced chemical shifts 1 15/14 N( 31 P) were determined for all compounds at natural abundance of 15 N by using Hahn-echo extended polarization transfer experiments.…”