Steps on the way to the first dirhodium tetracarboxylate with no axial ligation: Synthetic lessons and a plethora of Rh2(O2CR)4L2-n compounds, n=0, 1, 2

F. Albert Cotton, Elizabeth A. Hillard, Chun Y. Liu, Carlos A. Murillo, Wenning Wang, Xiaoping Wang

Research output: Contribution to journalArticlepeer-review

35 Scopus citations

Abstract

We report the preparation and structural features of thirteen new dirhodium tetracarboxylato compounds. Twelve of these were synthesized in early attempts to create Rh2(TiPB)4, where TiPB=2,4,6-triisopropylbenzoate, the first dirhodium tetracarboxylate without axial ligation, the structure of which is also reported here. Several challenges in the synthesis of such a molecule are identified and discussed. Although axial interactions are of paramount importance for Rh24+ units, Rh-Rh bond lengths are quite insensitive to the nature, presence or absence of axial ligation. However, the effect of axial ligation is clearly observed using electronic spectroscopy; Rh2(TiPB)4 shows an extremely low energy π*(Rh2)→σ*(Rh2) transition. The energy of this transition is put into the context of previously unreported spectroscopy of Rh2(O2CCPh3)4 bis-adducts.

Original languageEnglish
Pages (from-to)233-246
Number of pages14
JournalInorganica Chimica Acta
Volume337
DOIs
StatePublished - Sep 26 2002
Externally publishedYes

Funding

We thank the National Science Foundation for financial support. We thank Johnson-Matthey for a generous loan of RhCl 3 ·3H 2 O. E.A.H. thanks the National Science Foundation for a predoctoral fellowship.

Keywords

  • Axial ligation
  • Dirhodium
  • Electronic spectra
  • Metal carboxylates
  • Metal-metal bonds

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