Synthesis and molecular structures of fluorophosphoranes, R3PF2, isoelectronic with anionic fluorosilicates

Holmes, Robert R. ; Holmes, Joan M. ; Day, Roberta O. ; Kumara Swamy, K. C. ; Chandrasekhar, V. (1995) Synthesis and molecular structures of fluorophosphoranes, R3PF2, isoelectronic with anionic fluorosilicates Phosphorus, Sulfur, and Silicon and the Related Elements, 103 (1). pp. 153-169. ISSN 1042-6507

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Related URL: http://dx.doi.org/10.1080/10426509508027374

Abstract

The new difluorophosphoranes Ph(o-Tol)2PF2 (1), Mes3PF2 (2), Ph(I-Np)2PF2 (3), (o-Tol)3PF2, (p-Tol3PF2, Ph(t-Bu)2PF2, and (Ph2PF2CH2 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 suggests 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 crystallizes in the monoclinic space group C2/c with a = 11.819(3) Å, b = 10.163(2) Å, c = 13.992(3) Å, β = 99.14(2)°, and Z = 4.2 crystallizes in the monoclinic space group C2/c with a = 10.531(2) Å, b = 12.667(2) Å, c = 18.110(4) Å, β = 104.21(2)°, and Z = 4. 3 crystallizes in the monoclinic space group P21/c with a = 15.868(2) Å, b = 7.434(1) Å, c = 18.213(4) Å, β = 112.34(2)°, and Z = 4. The final conventional unweighted residuals are 0.063 (1), 0.060 (2), and 0.040 (3).

Item Type:Article
Source:Copyright of this article belongs to Taylor and Francis Ltd.
Keywords:Difluorophosphoranes; Anionic Fluorosilicates; X-ray Structures; NMR Spectra
ID Code:29631
Deposited On:23 Dec 2010 05:44
Last Modified:27 May 2011 09:34

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