Bulletin of the Korean Chemical Society

Korean Chemical Society (대한화학회)
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Synthesis and Structure of 1,2,3,4,5-Pentamethylcyclopentadienyl-1,4-Diphenyltetraazabutadiene Complexes of Rhodium and Iridium

  • Paek ,Cheolki (Department of Chemical Education, Korea National University of Education) ;
  • Ko, Jaejung (Department of Chemical Education, Korea National University of Education) ;
  • Kang, Sangook (Department of Chemistry, College of National Science, Korea University) ;
  • Patrick J.Carrol (Department of Chemistry,University of Pennsylvania)
  • Published : 1994.06.20
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Abstract

Monomeric rhodium and iridium-diaryltetrazene complexes $Cp^*$M(RNN=NNR)($Cp^*$=1,2,3,4,5-pentamethylcyclope ntadienyl; M=Rh, Ir; R=Ph, 4-tolyl) have been synthesized from [$Cp^*MCl_2]_2$(M=Rh, Ir) and 2 equiv. of $[Li(THF)_x]_2(RN_4$R) in benzene. We have determined the crystal structure of (${\eta}^5$-pentamethylcyclopentadienyl)diphenyltetrazene iridium by using graphite-monochromated Mo-$K_a$ radiation. The compound was crystallized in the monoclinic space group $P2_{1/c}$ with a=13.781(3), b=9.035(l), c=17.699(3) ${\AA}$, and ${\beta}=111.93(l)^{\circ}$. An X-ray crystal structure of complex 1 showed a short N(2)-N(3) distance ($1.265 {\AA}$) consistent with the valence tautomer A with Ir(III) rather than Ir(I). All complexes are highly colored and decompose on irradiation at 254 nm. Electrochemical studies show that complex 1 displays a quasi-reversible reduction.

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References

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