Chemischer InformationsdienstVolume 14, Issue 49 Physical Inorganic Chemistry ChemInform Abstract: GAS-PHASE MOLECULAR STRUCTURES OF BIS(DIFLUOROPHOSPHINO) SULFIDE, S(PF2)2, BIS(DIFLUOROPHOSPHINO) SELENIDE, SE(PF2)2, AND DIFLUORO(METHYLTHIO)PHOSPHINE, PF2(SME), DETERMINED BY ELECTRON DIFFRACTION D. E. J. ARNOLD, D. E. J. ARNOLDSearch for more papers by this authorG. GUNDERSEN, G. GUNDERSENSearch for more papers by this authorD. W. H. RANKIN, D. W. H. RANKINSearch for more papers by this authorH. E. ROBERTSON, H. E. ROBERTSONSearch for more papers by this author D. E. J. ARNOLD, D. E. J. ARNOLDSearch for more papers by this authorG. GUNDERSEN, G. GUNDERSENSearch for more papers by this authorD. W. H. RANKIN, D. W. H. RANKINSearch for more papers by this authorH. E. ROBERTSON, H. E. ROBERTSONSearch for more papers by this author First published: December 6, 1983 https://doi.org/10.1002/chin.198349002AboutPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Share a linkShare onFacebookTwitterLinked InRedditWechat No abstract is available for this article. Volume14, Issue49December 6, 1983 RelatedInformation

Chemischer InformationsdienstVolume 12, Issue 36 Physical Organic Chemistry ChemInform Abstract: NUCLEAR MAGNETIC RESONANCE SPECTRA OF SOME SILYL AND TRIMETHYLSILYL PSEUDOHALIDES D. E. J. ARNOLD, D. E. J. ARNOLDSearch for more papers by this authorS. CRADOCK, S. CRADOCKSearch for more papers by this authorE. A. EBSWORTH, E. A. EBSWORTHSearch for more papers by this authorJ. D. MURDOCH, J. D. MURDOCHSearch for more papers by this authorD. W. H. RANKIN, D. W. H. RANKINSearch for more papers by this authorD. C. J. SKEA, D. C. J. SKEASearch for more papers by this authorR. K. HARRIS, R. K. HARRISSearch for more papers by this authorB. J. KIMBER, B. J. KIMBERSearch for more papers by this author D. E. J. ARNOLD, D. E. J. ARNOLDSearch for more papers by this authorS. CRADOCK, S. CRADOCKSearch for more papers by this authorE. A. EBSWORTH, E. A. EBSWORTHSearch for more papers by this authorJ. D. MURDOCH, J. D. MURDOCHSearch for more papers by this authorD. W. H. RANKIN, D. W. H. RANKINSearch for more papers by this authorD. C. J. SKEA, D. C. J. SKEASearch for more papers by this authorR. K. HARRIS, R. K. HARRISSearch for more papers by this authorB. J. KIMBER, B. J. KIMBERSearch for more papers by this author First published: September 8, 1981 https://doi.org/10.1002/chin.198136049Read the full textAboutPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Share a linkShare onFacebookTwitterLinked InRedditWechat No abstract is available for this article. Volume12, Issue36September 8, 1981 RelatedInformation

The molecular structure of N(PF2)3 in the gas phase has been determined by electron diffraction. The molecule has a planar skeleton, with overall C3h symmetry, and ra(P–F) 157.4(2), ra(P–N) 171.2(4) pm, F–P–F 97.1(5), and F–P–N 99.0(4)°. The root-mean-square amplitude of torsion of the PF2 groups from their average positions is 17°, corresponding to a harmonic torsional frequency at 30 cm–1.

The moleculargeometryofdiaminodifluorophosphorane, PF2H(NH2)2, in the gas phase, has been studied by electron diffraction. A trigonal-bipyramidal structure is found, with axial fluorine atoms. Principal parameters are : ra( P–N) 164.0(5) pm; ra(P–F) 164.3(5) pm: HPF 89.3(8)°; HPN 118.8(5)°. Assuming these parameters, CNDO/2 calculations suggest that the P(NH2) groups are planar, and perpendicular to the equatorial plane of the trigonal bipyramid, and that the PNH angles are 124°. The molecule therefore has C2v symmetry.

AbstractDie Bis(difluorphosphino)chalkogenide (IIIa) und (IIIb) werden durch Austauschreaktionen von PXF, (X: Br, Cl) mit Y(SiH3), und Y(SnBu3)2 (Y: Se, S) dargestellt und durch Schwingungs‐, Massen‐, NMR‐ und Photoelektronenspektren charakterisiert.

Aminodifluorophosphine and boron trifluoride react in the gas or liquid phase to give an adduct, which decomposes into difluoro(difluorophosphinoamino)borane, BF2[NH(PF2)], which has been characterised by mass, photoelectron, n.m.r., and vibrational spectoscopy. With excess of PF2(NH2), the adduct reacts further to give bis(difluorophosphino)amine, NH(PF2)2, and the ammonia–trifluoroborane adduct.

AbstractPF2H(NH2 )2 wird in einem Schritt aus PClFz und NH3 dargestellt (Gleichung A) und NMR‐ (′H, ′9F, 31?), massen‐, schwingungs‐ und photoelektronenspektroskopisch charakterisiert.

AbstractDie Verbindungen (I) und (II) werden durch Reaktion in der Gasphase zwischen NH3, (CH3)3N und PClF2 erhalten.

Gas-phase electron-diffraction methods have been used to determine the molecular structure of bis(difluorophosphino)ether, F2POPF2. Most of the geometrical parameters are strongly correlated due to overlapping peaks in the radial distribution curve. In the structure that fits the experimental data most closely, the P-F and P-O bond lengths are 159.7 ± 0.4 and 153.3 ± 0.6 pm respectively, and the POP angle is 2.53 ± 0.02 rad (145°). The conformation is such that the molecule has no symmetry elements other than I (point group C1). In other refinements somewhat longer P-O and shorter P-F distances were obtained.

AbstractDie Reaktionen von PXFZ (X: Cl, Br) mit (MH3)2Y (M: Si, Ge; Y: O, S, Se, Te) werden NMR‐spektroskopisch untersucht.

AbstractDie durch Reaktion zwischen Silylbromid und Aminodifluorphosphin hergestellte Verbindung (I) zersetzt sich langsam bei Zimmertemperatur.

Silylaminodifluorophosphine has been prepared in high yield from the reaction between silyl bromide and aminodifluorophosphine; the compound decomposes slowly at room temperature. Its i.r. spectrum indicates that there are two conformers in the vapour at room temperature, but that in the solid at 77 K one conformer is much the more stable; the electron diffraction pattern of the vapour can also be interpreted in terms of the presence of two conformers, in each of which there are short H⋯F non-bonded distances. In each conformer the main structural parameters are taken to be the same, and are found to be : r(Si–N)= 1·720 ± 0·008; r(N–P)= 1·657 ± 0·007; r(P–F)= 1·574 ± 0·003 Å; ∠SiNP = 127·9 ± 0·7°; ∠FPF = 100·8 ± 1·2°; ∠FPN = 95·6°. The n.m.r. spectra (1H,19F) of SiH314NHPF2 and SiH315NHPF2 at room temperature show that the SiH protons behave as equivalent, as do the F nuclei, and that any NH exchange is slow on the n.m.r. timescale.

The reactions of PF2X (X = Cl or Br) with (MH3)2Y (M = Si or Ge; Y = O, S, Se, or Te) have been studied by n.m.r. spectroscopy. When X = Br and Y = S, Se, or Te, reaction occurs at room temperature to give the species MH3YPF2, (PF2)2Y, and MH3Br. 19F and 1H N.m.r. and double-resonance techniques have been used to determine the chemical shifts (1H, 19F, 31P, and 77Se) and coupling constants (including relative signs) of the products. The PF2Se– and PF2Te– compounds have exceptionally low 31P chemical shifts. The 19F spectrum of (PF2)2Se has been studied over a wide range of temperatures, and 2J(PP) and both 4J(FF) values are found to be strongly temperature-dependent. The 1H spectrum of SiH3TePF2 is also temperature-dependent.