- 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)]...
-
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.
- Boshaala, Ahmed M. A.,Simpson, Stephen J.,Autschbach, Jochen,Zheng, Shaohui
-
-
Read Online
- Thermal and photolytic substitution of ditechnetium and dirhenium decacarbonyl with trifluorophosphine
-
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
- Grimm, Casey C.,Clark, Ronald J.
-
-
Read Online
- +[Al(ORF)4]-, the salt of a homopolyatomic phosphorus cation
-
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
- Koechner, Tobias,Engesser, Tobias A.,Scherer, Harald,Plattner, Dietmar A.,Steffani, Alberto,Krossing, Ingo
-
-
Read Online
- Isolable N-heterocyclic carbene adducts of the elusive diiodophosphine
-
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.
- Cica?-Hudi,Schlindwein,Feil,Nieger,Gudat
-
-
Read Online
- PREPARATION AND NUCLEAR MAGNETIC RESONANCE SPECTRA OF AMINODIFLUOROPHOSPORANE
-
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.
- Rankin, David W. H.,Wright, John G.
-
-
Read Online
- The Preparation and Characterization by Raman Spectroscopy of PI4+AsF6- containing the Tetraiodophosphonium Cation
-
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.
- Tornieporth-Oetting, Inis,Klapoetke, Thomas
-
-
Read Online
- EPR Spectrum of CuPF3
-
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%.
- Histed, M.,Howard, J. A.,Jones, R.,Tomietto, M.
-
-
Read Online
- Infrared and Raman spectra, conformational stability, structural parameters, ab initio calculations and vibrational assignments of aminodifluorophosphine
-
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.
- Durig, James R.,Tschudin, Pamela,Cohn, Kim C.,Durig, Bryan R.,Zhou, Xiaohua,Zheng, Chao,El Defrawy, Ahmed M.
-
-
Read Online
- 1,3,2-Dithiaphospholanes with an annelated 1,2-dicarba-closo- dodecaborane(12) unit: Formation and reactivity
-
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.
- Wrackmeyer, Bernd,Klimkina, Elena V.,Milius, Wolfgang
-
p. 5021 - 5043
(2014/04/03)
-
- Chloro(trifluorophosphane)gold(I): [Au(PF3)Cl]
-
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
- Schoedel, Frauke,Bolte, Michael,Wagner, Matthias,Lerner, Hans-Wolfram
-
p. 652 - 654
(2008/10/09)
-
- NMR study of the interaction of tin(II) and antimony(III) fluorides with phosphorus chlorides
-
Reactions of SnF2 and SbF3 with POCl3 and PCl5 in acetonitrile were studied by 19F, 31P, and 119Sn NMR. Tetrahedral compounds POF2Cl and POF 3 form in the r
- Kokunov,Ershova,Razgonyaeva
-
p. 461 - 463
(2008/10/08)
-
- Synthesis and Characterization of the Platinum Cluster Complex Pt4(PF3)8
-
At temperatures approaching 200°C, Pt(PF3)4 loses PF3 and yields a cluster, Pt4(PF3)8. This composition has been confirmed by Fourier transform ion cyclotron resonance mass spectrometry, but its structure is unknown. At higher temperature, the monomer yields platinum metal (confirmed by X-ray diffraction) and the expected quantity of PF3 gas. The PF3 produced contains no observable impurities. Ligands such as olefins do not replace the PF3 in Pt(PF3)4. However, ligands like P(OCH3)3 cause extensive replacement of the PF3 ligand.
- Hammill, Cynthia L.,Clark, Ronald J.,Ross, Charles W. III,Marshall, Alan G.,Schmutz, James
-
p. 5973 - 5977
(2008/10/09)
-
- Thermal and photolytic substitution of dimanganese decacarbonyl with trifluorophosphine
-
Under thermal conditions, the PF3 substitution of Mn2(CO)10 produces five different compounds: 1-Mn2(CO)9(PF3), 1,1′-Mn2(CO)8(PF3)2, 1,2-Mn2(CO)8(PF3)2, 1,1′,2-Mn2(CO)7(PF3)3, and 1,1′,2,2′-Mn2-(CO)6(PF3) 4. Photolytic excitation results in the formation of four additional compounds. Substitution is rigorously limited to the replacement of four carbon monoxides, but that replacement is fairly readily achieved. Compounds are identified by using a combination of GC-MS, 19F NMR, and IR. Back reaction of 1,1′,2,2′-Mn2(CO)6(PF3)4 with 13CO produces only the previously observed PF3-substituted compounds having extensive label. Side products produced include the monometallic hydride series HMn(CO)5-x(PF3)x (x = 1-5), the hydrogen-bridged series Mn2(μ-H)(μ-PF2) (CO)8-x(PF3)x (x = 2-5), and the bisphosphido-bridged series Mn2(μ-PF2)2(CO)8-x(PF 3)x (x = 2-7).
- Grimm, Casey C.,Brotman, Paul E.,Clark, Ronald J.
-
p. 1119 - 1123
(2008/10/08)
-
- Gas-Phase Organometallic Chemistry of Ni(1+), NiCO(1+), NiPF3(1+), and NiC5H5(1+) with Aromatic Compounds
-
The gas-phase chemistry of Ni(1+) and the monoligated nickel cations NiCO(1+), NiPF3(1+), and NiC5H5(1+) with a series of aromatic compounds is reported here.The phenyl group is largely unreactive and does not appear to prohibit the metal ion from interacting with other parts of these molecules.For some phenyl compounds, C6H5X, no reaction is observed for Ni(1+).When Ni(1+) does react, products such as NiC6H4(1+) and NiC5H5(1+) are formed-depending on the chemical composition of the attached functional group (X).Ni+ reacts with benzyl compounds by insertion into the C6H5CH2-X bond, frequently followed by charge transfer to form C7H7(1+) as a product.The Ni(1+) ion is observed to decarbonylate aromatic carbonyl compounds.When a single ligand is attached to the Ni(1+), changes in the chemistry are observed.In many cases, the reactivity decreases as the size of ligand increases, suggesting the importance of steric interactions even for these monoligated species.There are some exceptions, where NiC5H5(1+) is most reactive, even thought the cyclopentadienyl ligand is the largest.It is suggested that some charge transfer may occur in NiC5H5(1+), resulting in increased positive charge on the metal, loading to increased reactivity.
- Stepnowski, Richard,Allison, John
-
p. 449 - 457
(2007/10/02)
-
- Formation and NMR Spectroscopic Characterization of the Fluorophosphonium Cations, PH4-nFn+ (n = 1-4)
-
The preparations of the salts PH3F+SbF6- and PHF3+Sb2F11- are reported.All fluorophosphonium cations PH4-nFn+ are characterized by multinuclear (1H, 19F, 31P) NMR spectroscopy.For n > 1 these salts are easily accessible by fluoride abstraction from fluorohydridophosphates(V).PH3F+SbF6-, however, is obtained in the reaction of PH3F2 with SbF5. - keywords: Fluorophosphonium Salts, Formation, NMR Spectra
- Minkwitz, Rolf,Liedtke, Andreas
-
p. 679 - 682
(2007/10/02)
-
- Preparation of new bis(dialkylamino)phosphine species via reduction of bis(dialkylamino)halophosphines
-
Four new bis(dialkylamino)phosphine species, (Me2N)2PH, CH3NCH2CH2N(CH3)PH, (CO)3Ni[(Me2N)2PH], and (CO)3Ni-[CH3NCH2CH2N(CH 3)PH], have easily been prepared in good yields through reduction of corresponding bis(dialkylamino)-halophosphines by lithium tri-sec-butylborohydride. The preparation and characterization of these compounds are discussed. An improved synthesis for obtaining quantitative yields of (CO)3NiL [L = Me2NPF2, (Me2N)2PF, CH3NCH2CH2N(CH3)PF] is also described.
- Snow, Sarah S.,Jiang, De-Xiang,Parry, Robert W.
-
p. 1460 - 1463
(2008/10/08)
-
- Trifluoromethyl Group 2B Compounds: Bis(trifluoromethylcadmium*Base. New, More Powerful Ligand-Exchange Reagents and Low Temperature Difluorocarbene Sources
-
Lewis base adducts of bis(trifluoromethyl)cadmium have been isolated from the interaction of bis(trifluoromethyl)mercury with dimethylcadmium in solvents like THF, glyme, diglyme, or pyridine.Lewis base exchange, for example, pyridine for glyme, occurs upon dissolution of the glyme adduct, (CF3)2Cd*g, g = CH3OCH2CH2OCH3, in pyridine.The (CF3)2Cd*base species are shown to be much more reactive than (CF3)2Hg since the cadmium compounds are reactive at temperatures at least 100 deg C below that required for the mercurial.At ambient temperatures ligand exchanges between SnBr4 or GeI4 and (CF3)2Cd*glyme are found to be most convenient preparations of (CF3)4Sn (66percent yield) or (CF3)4Ge (43percent yield); the formation of (CF3)3P from the reaction of PI3 also occurs, but the amounts isolated are smaller.The reaction of acyl halides with (CF3)2Cd*g proceeds at subambient temperature to yield the acyl fluoride, ca. 90percent yield, and difluorocarbene which can be trapped stereospecifically by, e.g., cis-2-butene at -30 deg C.Difluorocarbene formation occurs at temperatures at least as low as -78 deg C.
- Krause, L. J.,Morrison, J. A.
-
p. 2995 - 3001
(2007/10/02)
-
- Reactivity of transition metal fluorides. II. Uranium hexafluoride
-
Reactions have been studied between uranium hexafluoride and a series of lower fluorides of other elements. The study has also included reaction with a wide range of covalent chlorides. The reactivity of uranium hexafluoride is compared with that of the higher fluorides of d-transition elements, chromium, molybdenum, and tungsten, and considered in the light of uranium as an f-transition element.
- O'Donnell,Stewart,Wilson
-
p. 1438 - 1441
(2008/10/08)
-
- Reactivity of transition metal fluorides. III. Higher fluorides of vanadium, niobium, and tantalum
-
A series of oxidation-reduction and halogen-exchange reactions has been used to compare the chemical reactivities of the pentafluorides of vanadium, niobium, and tantalum. Vanadium pentafluoride is extremely reactive and its reaction pattern with many reagents is extremely complex, depending largely on relative proportions of reagents and other experimental conditions. The pentafluorides of niobium and tantalum are very much less reactive than that of vanadium and are similar to each other. There is some evidence that of the two, the niobium compound is slightly more reactive. The reactivities of these three pentafluorides are discussed in terms of their physical properties and in relation to the higher fluorides of neighboring transition elements.
- Canterford,O'Donnell
-
p. 1442 - 1446
(2008/10/08)
-
- Further studies of the tetraborane carbonyl B4H8CO
-
Tetraborane-8 carbonyl (B4H8CO) is made by the action of CO on either B4H10 or B5H11, suggesting the processes B4H10 → B4H8 + H2 and B5H11 → B4H8 + BH3. The reversal of these (significant for polyborane interconversion mechanisms) is shown by the high yields of B4H10 and B5H11 obtained when H2 or B2H6 reacts with B4H8CO. Basic reagents attack B4H8CO to form nonvolatiles without liberation of any CO; dimethyl ether and water behave so, and trimethylamine forms some (CH3)3NBH3. Ethylene also fixes the CO, in a slightly volatile unstable compound, (C2H4)4B4H8CO (structure uncertain), whereas BH3CO + 3C2H4 → (C2H5)3B + CO is quantitative. With excess PF3, B5H11 forms BH3PF3 and B4H8PF3, from the latter of which CO reversibly displaces PF3; in these reactions CO is not irreversibly fixed. In support of structural elucidation of B4H8CO by infrared and nuclear magnetic resonance spectra, B4D10, B5D11, and B4D8CO were made in nearly pure form. The structure of B4H8CO remains uncertain but the possibilities are limited. There may be a tautomeric equilibrium such that at least one H atom alternates between two B-H-B bridgings and a terminal B-H situation - much like the tautomerism of B5H11.
- Spielman, John R.,Burg, Anton B.
-
p. 1139 - 1145
(2008/10/08)
-
