57368-25-9Relevant academic research and scientific papers
SYNTHESIS AND MOLECULAR STRUCTURES OF FLUOROPHOSPHORANES, R3PF2, ISOELECTRONIC WITH ANIONIC FLUOROSILICATES
Holmes, Robert R.,Holmes, Joan M.,Day, Roberta O.,Swamy, K. C. Kumara,Chandrasekhar, V.
, p. 153 - 170 (2007/10/02)
The new difluorophosphoranes Ph(o-Tol)2PF2 (1), Mes3PF2 (2), Ph(1-Np)2PF2 (3), (o-Tol)3PF2, (p-Tol)3PF2, Ph(t-Bu)2PF2, and (Ph2PF2)2CH2 containing bulky substituents were prepared by the fluorination reaction of precursor organophosphines with dimethylaminosulfur trifluoride.They were characterized by 1H, 31P, and 19F NMR spectra.The molecular structures of 1-3 revealed trigonal bipyramidal geometries.Comparison of the structural data with that of isoelectronic anionic fluorosilicates along with the NMR data suggest the operation of a steric effect that increases bond lengths in the difluorophosphoranes 1-3 and in related anionic silicates.The data are discussed relative to enhanced reactivity observed for anionic silicates. 1 cryatallizes in the monoclinic space group C2/c with a = 11.819(3) Angstroem, b = 10.163(2) Angstroem, c = 13.992 Angstroem, β = 99.14(2) deg, and Z = 4. 2 crystallizes in the monoclonic space group C2/c with a = 10.531(2) Angstroem, b = 12.667(2) Angstroem, c = 18.110(4) Angstroem, β = 104.21(2) deg, and Z = 4. 3 crystallizes in the monoclinic space group P21/c with a = 15.868(2) Angstroem, b = 7.434(1) Angstroem, c = 18.213(4) Angstroem, β = 112.34(2) deg, and Z = 4.The final conventional unweighted residuals are 0.063 (1), 0.060 (2), and 0.040 (3).Key words: Difluorophosphoranes, anionic fluorosilicates, x-ray structures, NMR spectra
The Synthesis and Structural Characterization of Mesityldiphenylphosphine, Dimesitylphenylphosphine and Trimesitylphosphine
Blount, John F.,Camp, David,Hart, Robert D.,Healy, Peter C.,Skelton, Brian W.,White, Allan H.
, p. 1631 - 1640 (2007/10/02)
The synthesis and structural characterization of the tertiary phosphines mesityldiphenylphosphine , dimesitylphenylphosphine and a new phase of trimesitylphosphine have been carried out.Crystals of PPh2(mes) are monoclinic, space group P21/c, with a 10.252(10), b 9.847(11), c 17.444(7) Angstroem, β 99.78(6) deg, Z 4; R 0.059 for 2102 "observed" reflections.Crystals of PPh(mes)2 are also monoclinic, space group P21/c, with a 8.964(9), b 22.99(1), c 10.228(4) Angstroem, β 107.98(5) deg, Z 4; R 0.058 for 2350 "observed" reflections.The new phase of P(mes)3 is monoclinic, Cc, a 11.390(5), b 12.034(4), c 17.564(9) Angstroem, β 104.22(4) deg, Z 4 (R 0.060 for 1046 "observed" reflections), in which the molecule is disordered.A full report is given for the phase previously studied (triclinic), P, a 8.191(3), b 16.447(5), c 18.667(6) Angstroem, α 104.82(3), β 97.74(3), γ 100.07(3) deg, Z 4; R 0.065 for 4964 "observed" reflections.The P-C bond distances are similar for the whole series of compounds with an average value of 1.833(1) Angstroem.Introduction of the mesityl groups results in an increase of the C-P-C angles from c. 103 to c. 110 deg with a concomitant flattening of the PC3 pyramid.
