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Oxotrichlorobis(triphenylphosphine)rhenium(V)

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Oxotrichlorobis(triphenyl-
phosphine)rhenium(V)
Names
IUPAC name
Trichloridooxidobis(triphenylphosphane)rhenium(V)
Identifiers
3D model (JSmol)
ChemSpider
  • 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;/p-3
    Key: ZHLPLZVSIOQWFP-UHFFFAOYSA-K
  • C1=CC=C(C=C1)P(C2=CC=CC=C2)C3=CC=CC=C3.C1=CC=C(C=C1)P(C2=CC=CC=C2)C3=CC=CC=C3.[O-2].[Cl-].[Cl-].[Cl-].[Re]
Properties
ReOCl3(PPh3)2
Molar mass 833.15 g/mol
Appearance yellow microcrystals
Melting point 205 °C (401 °F; 478 K)
not soluble in water
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
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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.[1] 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 d2.

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.[2]

ReOCl3(PPh3)2 catalyzes the selective oxidation of secondary alcohols by DMSO, producing the corresponding ketals.[3]

References

  1. ^ Johnson, N. P.; Lock, C. J. L.; Wilkinson, G. (1967). "Complexes Of Rhenium(V)". Inorg. Synth. Inorganic Syntheses. 9: 145. doi:10.1002/9780470132401.ch39. ISBN 978-0-470-13240-1.
  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
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