Isolation and spectral studies of water-soluble eta(5)-cyclichydrocarbon rhodium and iridium complexes with pyridyl diketone analogues bonded through kappa(2)-N boolean AND O, kappa(4)-N boolean AND O, and kappa(3)-N-C-N modes

作者：Nongbri Saphidabha L; Das Babulal; Rao Kollipara Mohan^*

来源：Journal of Coordination Chemistry, 2012, 65(5): 875-890.

DOI：10.1080/00958972.2012.664638

• 1-Phenyl-3-(2-pyridyl)propane-1,3-dione
• 1,3-Di(2-pyridyl)propane-1,3-dione
• Rhodium
• Iridium
• Pentamethylcyclopentadienyl
• C-H activation

The reaction of [Cp*M(mu-Cl)Cl](2) (M = Rh, Ir; Cp* = eta(5)-C5Me5) with 1-phenyl-3-(2-pyridyl) propane-1,3-dione (pppdH) and 1,3-di(2-pyridyl) propane-1,3-dione (dppdH) in 1 : 2 and 1 : 1 molar ratio, respectively, yielded corresponding monomeric complexes [Cp*M(kappa(2)-N-O-pppdH)Cl](+) [M = Rh (1), Ir (2)] and dimeric complexes [(Cp*)(2)M-2(kappa(4)-N-O-dppd)Cl-2](+) [M = Rh (3), Ir (4)]. The treatment of [Cp*Ir(mu-Cl)Cl](2) with dppdH in 1 : 2 molar ratio yielded the activated monomeric complex [Cp*Ir(kappa(3)-N-C-N-dppd)](+) (5). The formation of a C(sp(3))-H is attributed to softer iridium, whereas Cp*Rh precursor yielded only the corresponding dimer 3. The formation of these complexes has been established by IR and NMR spectroscopic data and elemental analysis. Molecular structures of 2, 3, and 5 have been confirmed by single-crystal X-ray diffraction. The enolic "O-C-C-C-O" fragment of the coordinated ligand is neutral (kappa(2)-N-O-pppdH) in monomeric 1 and 2 and neutral as well as concomitantly uninegative (kappa(4)-N-O-dppd) in dimeric 3 and 4. In C-H-activated monomeric complex 5, the "O-C-C-C-O" fragment is in ketonic form with (kappa(3)-N-C-N-dppd) bonding of the ligand.

• 出版日期2012