7783-55-3Relevant articles and documents
Synthesis and characterization of the trihalophosphine compounds of ruthenium [RuX2(η6-cymene)(PY3)] (X = Cl, Br, Y = F, Cl, Br) and the related PF2(NMe2) and P(NMe2)3 compounds; multinuclear NMR spectroscopy and the X-ray single crystal structures of [RuBr2(η6-cymene) (PF3)]...
Boshaala, Ahmed M. A.,Simpson, Stephen J.,Autschbach, Jochen,Zheng, Shaohui
, p. 9279 - 9292 (2008)
Full title: Synthesis and characterization of the trihalophosphine compounds of ruthenium [RuX2(η6-cymene)(PY3)] (X = Cl, Br, Y = F, Cl, Br) and the related PF2(NMe2) and P(NMe2)3 compounds; multinuclear NMR spectroscopy and the X-ray single crystal structures of [RuBr2(η6-cymene) (PF3)], [RuBr2(η6-cymene)(PF 2{NMe2})]. Treatment of the dimers [RuX2(η6-cymene)] 2 with PF3 in hot heptane produces the compounds [RuX 2(η6-cymene)(PF3)] (X = Cl, Br, I) in good yield. Difluoro(dimethylamino)phosphine and tris(dimethylamino)phosphine react similarly to produce the compounds [RuX2(η6-cymene) (PF2{NMe2})] and [RuX2(η6- cymene)(P{NMe2}3)]. Reaction of the dimers [RuX 2(η6-cymene)]2 with PCl3 and PBr3 proceeded with the production of mononuclear products which had undergone halogen exchange at ruthenium in some cases. 1H, 13C, 31P, and 19F NMR spectra have been obtained where appropriate together with (1H-1H) correlation spectroscopy (COSY) and (13C-1H)-HETCORR spectra of selected compounds. The variation of 1J( 31P-19F) with the nature of the auxiliary ligand (X) in the PF3 and PF2(NMe2) complexes has been examined both experimentally and computationally using a natural localized molecular orbital-natural bond order approach. The single crystal X-ray structure of [RuBr2(η6-cymene)(PF3)] has been determined at 223 K and those of [RuBr2(η6- cymene)(PF2{NMe2})] and [RuI2(η 6-cymene)(P{NMe2}3)] at 294 K.
Thermal and photolytic substitution of ditechnetium and dirhenium decacarbonyl with trifluorophosphine
Grimm, Casey C.,Clark, Ronald J.
, p. 1123 - 1127 (1990)
The substitution reaction of Tc2(CO)10 and Re2(CO)10 with PF3 has been studied under both thermal and photolytic conditions. Complete substitution was not observed for either system. Substitution of u
+[Al(ORF)4]-, the salt of a homopolyatomic phosphorus cation
Koechner, Tobias,Engesser, Tobias A.,Scherer, Harald,Plattner, Dietmar A.,Steffani, Alberto,Krossing, Ingo
, p. 6529 - 6531 (2012)
Positive at last: The first condensed-phase homopolyatomic phosphorus cation [P9]+ was prepared using a combination of the oxidant [NO]+ and weakly coordinating anion, [Al{OC(CF 3)3}4]-. [P9]+ consists of two P5 cages linked by a phosphonium atom to give a D2d-symmetric Zintl cluster. NMR (see picture), Raman, and IR spectroscopy, mass spectrometry, and quantum-chemical calculations confirmed the structure. Copyright
Isolable N-heterocyclic carbene adducts of the elusive diiodophosphine
Cica?-Hudi,Schlindwein,Feil,Nieger,Gudat
, p. 7645 - 7648 (2018)
Reactions of PH-substituted phosphinidene-imidazolylidenes with I2 afford isolable NHC-adducts of the transient diiodophosphine PHI2. The products, which show a surprising structural diversity, are according to DFT studies best formulated as charge-transfer complexes of onio-substituted cationic phosphines with I? and are capable of reaction under formal transfer of an NHC-P+ unit.
PREPARATION AND NUCLEAR MAGNETIC RESONANCE SPECTRA OF AMINODIFLUOROPHOSPORANE
Rankin, David W. H.,Wright, John G.
, p. 2049 - 2050 (1980)
Aminodifluorophosphorane has been prepared by the reaction in solution of difluorophosphine and ammonia.N.m.r. spectra indicate that the fluorine atoms are in axial positions and that the amino-group atoms lie in a plane perpendicular to the equatorial plane.At 215 K there is no evidence for rotation about the P-N bond or for fluxional behaviour.The compound is thermally unstable, and has not been isolated.
The Preparation and Characterization by Raman Spectroscopy of PI4+AsF6- containing the Tetraiodophosphonium Cation
Tornieporth-Oetting, Inis,Klapoetke, Thomas
, p. 132 - 133 (1990)
The thermodynamically unstable PI4+AsF6- containing the first and only example of a tetrahedral PI4+ cation, formally a derivative of the unknown PI5, was prepared by the reaction of PI3 and I3+AsF6- at low temperatures and characterized by Raman spectroscopy.
EPR Spectrum of CuPF3
Histed, M.,Howard, J. A.,Jones, R.,Tomietto, M.
, p. 1141 - 1143 (1992)
CuPF3 is formed from Cu atoms and PF3 on solid adamantane at 77 K in a rotating cryostat.It has the magnetic parameters a63 = 4205 +/- 10 MHz, a31 = 1100 +/- 10MHz, a19 = 90 +/- 10MHz, and g = 1.999 +/- 0.002, has a 2A1 electronic ground state in the point group C3v, and can be considered to be a copper-centered radical and not a phosphoranyl formed by addition of a Cu atom to PF3.About 70percent of the unpaired spin is located in the metal 4s orbital, 8percent in the P 3s orbital, and 0.5percent in the F 2s orbitals for a total unpaired spin s population of 78.5percent.The remaining 21.5percent of unpaired spin is probably located in Cu 4p orbital.Cu3 is also formed in adamantane and does not appear to react with PF3.Cu7 rather than CuPF3 is formed in solid cyclohexane and is also unreactive toward PF%.
Infrared and Raman spectra, conformational stability, structural parameters, ab initio calculations and vibrational assignments of aminodifluorophosphine
Durig, James R.,Tschudin, Pamela,Cohn, Kim C.,Durig, Bryan R.,Zhou, Xiaohua,Zheng, Chao,El Defrawy, Ahmed M.
, p. 406 - 418 (2008)
Infrared spectra (4000-50 cm-1) have been recorded for three isotopomers of aminodifluorophosphine, H2NPF2, H215NPF2 and D2NPF2, of the gases. The Raman spectra of all three molecules were recorded of the liquids. To support the vibrational assignment MP2(full) ab initio calculations with the 6-31G(d) basis set were carried out to predict the fundamental vibrational frequencies, infrared intensities, Raman activities, depolarization values and infrared band contours. Additional ab initio calculations employing a variety of basis sets with and without diffuse functions have been used to predict the conformational stability, structural parameters and centrifugal distortion constants. These predictions are compared to previously reported experimental values when available. The adjusted r0 structural parameters have been obtained by systematically fitting the MP2(full)/6-311+G(d) predicted values with the previously reported rotational constants for five isotopomers obtained from the microwave study. The difference in the two NH distances is 0.003 ? which is much smaller than the value of 0.021 ? previously reported. The bonding around the nitrogen atom is effectively planar which is consistent with the previously reported structural information from the microwave study but differs from the reported slightly pyramidal bonding obtained in the electron diffraction investigation. The adjusted r0 heavy atom distances and angles are: r(PF) = 1.587(3); r(NP) = 1.649(3) ?; ∠FPF = 94.7(5); ∠NPF = 100.6(5)°. Vibrational assignments are given for H2NPF2, H215NPF2 and D2NPF2 which are supported by ab initio MP2/6-31G(d) calculations. These results are compared to the corresponding quantities of some similar molecules.
1,3,2-Dithiaphospholanes with an annelated 1,2-dicarba-closo- dodecaborane(12) unit: Formation and reactivity
Wrackmeyer, Bernd,Klimkina, Elena V.,Milius, Wolfgang
, p. 5021 - 5043 (2014/04/03)
1,3,2-Dithiaphospholanes were prepared, containing an annelated 1,2-dicarba-closo-dodecaborane(12) unit, bearing halogens (F, Cl, Br, and I), H, NEt2, OEt groups, or organo substituents (R = i-Pr, t-Bu, Cy, 3,5-Me2-C6H3-CH2, Ph) at phosphorus. The t-Bu derivative was structurally characterised as its sulfide. The organo-substituted derivatives escape the ring strain by irreversible (R = t-Bu; X-ray analysis) or reversible dimerisation, by which 10-membered rings are formed. Using 1,1-bis(dichlorophosphino)methane, another dimer containing a 14-membered ring could be isolated and structurally characterised. The preferred conformation of the 1,3,2-dithiaphospholanes depends on the nature of the substituent at phosphorus. For instance, the substituents R = t-Bu, NEt 2 prefer the equatorial position, as indicated by diagnostic NMR data, supported by DFT calculations [B3LYP/6-311+G(d,p) level of theory]. The calculations also predict the tendency for dimerisation, and calculated NMR parameters are in good agreement, in most cases, with experimental data.
Chloro(trifluorophosphane)gold(I): [Au(PF3)Cl]
Schoedel, Frauke,Bolte, Michael,Wagner, Matthias,Lerner, Hans-Wolfram
, p. 652 - 654 (2008/10/09)
X-ray quality crystals of [Au(PF3)Cl] (orthorhombic, Pnma) are obtained from a toluene / pentane solution at 6 °C. According to the result of the X-ray structural analysis, [Au(PF3)Cl] contains an almost linear F3P-Au-Cl u
