Main-Group-Organotransition-Metal Chemistry: The Cyclopentadienylchromium Polyiodides Including [(C5Me5)2Cr2I3+]2[I162-]

David B. Morse, Thomas Rauchfuss, Scott R. Wilson

Research output: Contribution to journalArticlepeer-review

Abstract

The reaction of [Cp*Cr(CO)2]2 (Cp* = η5-C5Me5) and I2 affords a compound of the empirical formula Cp*CrI3 (2). Single-crystal X-ray diffraction shows 2 to be a polymer, {[Cp*CrI(μ-I)]2·[Cp*Cr(I 3)(μ-I)]2}n [monoclinic P21/c; a = 15.658 (2), b = 8.504 (1), c = 23.242 (4) Å; β = 102.48 (1)°; V = 3021.7 (9) Å3; Z = 2; ρPcalc = 2.497 g cm-3; 3014 observed reflections I > 2.58σ(I); R = 0.039, Rw = 0.041]. 1H NMR studies show that in chlorinated solvents 2 dissociates into [Cp*CrI(μ-I)]2 (1), the latter of which can be prepared by reduction of 2 with Zn/Hg. Treatment of 2 with high concentrations of I2 (I/Cr of >6) gives Cp*CrI5.5 (3), which is formulated as [Cp*2Cr2(μ-I)3]2[I 16] [monoclinic, P21/c; a = 14.744 (2), b = 22.864 (4), c = 23.267 (5) Å; β = 93.77 (2)°; V = 7827 (4) Å3, Z = 4; ρcalc = 3.005 g cm-3; 6153 observed reflections I > 2.58σ(I); R = 0.054, Rw = 0.063]. The cation exhibits a short Cr-Cr distance of 3.00 (1) Å indicative of Cr(III)-Cr(III) bonding. This cation is imbedded within a three-dimensional polyiodide lattice based upon I162- subunits. The I162- cluster is comprised of an I2-linked pair of roughly planar (I2)3I- subunits.

Original languageEnglish (US)
Pages (from-to)1860-1864
Number of pages5
JournalJournal of the American Chemical Society
Volume112
Issue number5
DOIs
StatePublished - Jan 1990

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

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