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 language | English |
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Pages (from-to) | 233-246 |
Number of pages | 14 |
Journal | Inorganica Chimica Acta |
Volume | 337 |
DOIs | |
State | Published - Sep 26 2002 |
Externally published | Yes |
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