Adduct Polymers and Dimers of Rhodium(II) Pivalate with Pyrazine, 4,4′-Bipyridine, 1,4-Diazabicyclo[2.2.2]octane, Triethylamine, and Pyridine

• Published in: Bulletin of the Chemical Society of Japan Vol. 72; no. 12; pp. 2681 - 2686
• Main Authors: Handa, Makoto, Watanabe, Mayumi, Yoshioka, Daisuke, Kawabata, Seiichiro, Nukada, Ryoji, Mikuriya, Masahiro, Azuma, Hiroshi, Kasuga, Kuninobu
• Format: Journal Article
• Language: English
• Published: Tokyo The Chemical Society of Japan 01.12.1999; Chemical Society of Japan
• ISSN: 0009-2673; 1348-0634
• DOI: 10.1246/bcsj.72.2681

Adducts of rhodium(II) pivalate with pyrazine (pyz), 4,4′-bipyridine (4,4′-bpy), and 1,4-diazabicyclo[2.2.2]octane (dabco), triethylamine (tea), and pyridine (py) have been prepared. The adducts with pyz, 4,4′-bpy, and dabco are polymers formulated as [Rh2(O2CCMe3)4(L)]n, (L = pyz, 4,4′-bpy, and dabco). A polymer structure with an alternating arrangement of the rhodium(II) dimer and ligands was confirmed by an X-ray structure analysis of the 4,4′-bpy adduct. The Rh–Rh bond distance is 2.395(1) Å which is in the range of those reported for the adducts of rhodium(II) carboxylates with axial aromatic nitrogen-donor ligands. The structure of the adduct dimers, [Rh2(O2CCMe3)4(L)2] (L = tea and py), was also confirmed for a tea-coordinated complex, which has considerably long axial Rh–N (2.391(8) Å) and Rh–Rh (2.413(1) Å) bonds. The reflectance-spectral and thermogravimetric data of all the adducts were obtained to examine the axial interaction between the rhodium(II) dimer core and the ligands.