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Oxotrichlorobis(triphenylphosphine)rhenium(V)

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Oxotrichlorobis(triphenyl­phosphine)rhenium(V)
Names
IUPAC name Trichloridooxidobis(triphenylphosphane)rhenium(V)
Identifiers
CAS Number
3D model (JSmol)
ChemSpider
PubChem CID
InChI
  • InChI=1S/2C18H15P.3ClH.O.Re/c2*1-4-10-16(11-5-1)19(17-12-6-2-7-13-17)18-14-8-3-9-15-18;;;;;/h2*1-15H;3*1H;;/q;;;;;-2;+5/p-3Key: QYKOBCZMNRLXRH-UHFFFAOYSA-K
SMILES
  • Cl(Cl)(Cl)(=O)((c1ccccc1)(c1ccccc1)c1ccccc1)(c2ccccc2)(c2ccccc2)c2ccccc2
  • C1(P(C2=CC=CC=C2)C3=CC=CC=C3)=CC=CC=C1.C4(P(C5=CC=CC=C5)C6=CC=CC=C6)=CC=CC=C4.....
Properties
Chemical formula ReOCl3(PPh3)2
Molar mass 833.15 g/mol
Appearance yellow microcrystals
Melting point 205 °C (401 °F; 478 K)
Solubility in water not soluble in water
Except where otherwise noted, data are given for materials in their standard state (at 25 °C , 100 kPa). checkverify (what is  ?) Infobox references
Chemical compound

Oxotrichlorobis(triphenylphosphine)rhenium(V) is the chemical compound with the formula ReOCl3(PPh3)2. This yellow, air-stable solid is a precursor to a variety of other rhenium complexes. In this diamagnetic compound, Re has an octahedral coordination environment with one oxo, three chloro and two mutually trans triphenylphosphine ligands. The oxidation state of rhenium is +5 and its configuration is d.

Synthesis

ReOCl3(PPh3)2 is commercially available, but it is readily synthesized by reaction of perrhenic acid with triphenylphosphine in a mixture of hydrochloric acid and acetic acid. In this reaction, Re(VII) is reduced to Re(V), and triphenylphosphine is oxidized to its oxide.

HReO4 + 3 HCl + 3 PPh3 → ReOCl3(PPh3)2 + Ph3PO + 2 H2O

The required perrhenic acid solution can be prepared in situ from rhenium(VII) oxide.

Uses

ReOCl3(PPh3)2 is a precursor to a variety of other oxo-, nitridio, and hydrido complexes. It converts to ReH7(PPh3)2 by a treatment with LiAlH4.

ReOCl3(PPh3)2 catalyzes the selective oxidation of secondary alcohols by DMSO, producing the corresponding ketals.

References

  1. Johnson, N. P.; Lock, C. J. L.; Wilkinson, G. (1967). "Complexes of Rhenium(V)". Inorganic Syntheses. Vol. 9. pp. 145–148. doi:10.1002/9780470132401.ch39. ISBN 978-0-470-13240-1. {{cite book}}: |journal= ignored (help)
  2. K. Abdur-Rashid; A. J. Lough & R. H. Morris (2001). "Intra- and inter-ion-pair protonic-hydridic bonding in polyhydridobis(phosphine)rhenates". Canadian Journal of Chemistry. 79 (5–6): 964. doi:10.1139/cjc-79-5-6-964.
  3. Pombeiro, A. J. L.; Fatima, M.; Crabtree, R. H. "Technetium and Rhenium: Inorganic & Coordination Chemistry" Encyclopedia of Inorganic Chemistry. John Wiley & Sons: New York, 2006. doi:10.1002/0470862106.ia237
Rhenium compounds
Rhenium(0)
Organorhenium(0)
Rhenium(I)
Organorhenium(I)
Rhenium(II)
Rhenium(III)
Rhenium(IV)
Rhenium(V)
Rhenium(VI)
Rhenium(VII)
Perrhenates
  • Re2O7(OH2)2
  • NH4ReO4
  • NaReO4
  • AgReO4
  • Organorhenium(VII)
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