Tapas Ghatak

Olefin Oxygenation by Water on an Iridium Center

Oxygenation of 1,5-cyclooctadiene (COD) is achieved on an iridium center using water as a reagent. A hydrogen-bonding interaction with an unbound nitrogen atom of the naphthyridine-based ligand architecture promotes nucleophilic attack of water to the metal-bound COD. Irida-oxetane and oxo-irida-allyl compounds are isolated, products which are normally accessed from reactions with H2O2 or O2. DFT studies support a ligand-assisted water activation mechanism.

Amide-functionalized naphthyridines on a Rh II –Rh II platform: effect of steric crowding, hemilability, and hydrogen-bonding interactions on the structural diversity and catalytic activity of dirhodium(II) complexes

Ferrocene-amide-functionalized 1,8-naphthyridine (NP) based ligands {[(5,7-dimethyl-1,8-naphthyridin-2-yl)amino]carbonyl}ferrocene (L(1) H) and {[(3-phenyl-1,8-naphthyridin-2-yl)amino]carbonyl}ferrocene (L(2) H) have been synthesized. Room-temperature treatment of both the ligands with Rh2 (CH3 COO)4 produced [Rh2 (CH3 COO)3 (L(1) )] (1) and [Rh2 (CH3 COO)3 (L(2) )] (2) as neutral complexes in which the ligands were deprotonated and bound in a tridentate fashion. The steric effect of the ortho-methyl group in L(1) H and the inertness of the bridging carboxylate groups prevented the incorporation of the second ligand on the {Rh(II) -Rh(II) } unit. The use of the more labile Rh2 (CF3 COO)4 salt with L(1) H produced a cis bis-adduct [Rh2 (CF3 COO)4 (L(1) H)(2) ] (3), whereas L(2) H resulted in a trans bis-adduct [Rh2 (CF3 COO)3 (L(2) )(L(2) H)] (4). Ligand L(1) H exhibits chelate binding in 3 and L(2) H forms a bridge-chelate mode in 4. Hydrogen-bonding interactions between the amide hydrogen and carboxylate oxygen atoms play an important role in the formation of these complexes. In the absence of this hydrogen-bonding interaction, both ligands bind axially as evident from the X-ray structure of [Rh2 (CH3 COO)2 (CH3 CN)4 (L(2) H)2 ](BF4 )2 (6). However, the axial ligands reorganize at reflux into a bridge-chelate coordination mode and produce [Rh2 (CH3 COO)2 (CH3 CN)2 (L(1) H)](BF4 )2 (5) and [Rh2 (CH3 COO)2 (L(2) H)2 ](BF4 )2 (7). Judicious selection of the dirhodium(II) precursors, choice of ligand, and adaptation of the correct reaction conditions affords 7, which features hemilabile amide side arms that occupy sites trans to the Rh-Rh bond. Consequently, this compound exhibits higher catalytic activity for carbene insertion to the CH bond of substituted indoles by using appropriate diazo compounds, whereas other compounds are far less reactive. Thus, this work demonstrates the utility of steric crowding, hemilability, and hydrogen-bonding functionalities to govern the structure and catalytic efficacyof dirhodium(II,II) compounds.

Cyclometalated Ir–Sn Construct for Cyanosilylation

Two cyclometalated compounds [IrIIICl{(2-biphenylene-1,8-naphthyridine-κC,N}(η5-pentamethylcyclopentadienyl)] (1) and [IrIIICl{(2-(2-N-Methyl-pyrrolyl-1,8-naphthyridine-κC,N}(η5-pentamethylcyclopentadienyl)] (2) containing naphthyridine based ligands have been synthesized in high yield. Insertion of SnCl2 to a terminal Ir–Cl bond of 1 affords the mixed Ir–SnCl3 compound [IrIIISnCl3{(2-biphenylene-1,8-naphthyridine-κC,N}(η5-pentamethylcyclopentadienyl)] (3). The heterobimetallic compound 3 is shown to be an excellent catalyst for a variety of cyanosilylation reactions. A cooperative mechanism has been proposed which involves the simultaneous activation of aldehyde and cyanide precursor by Sn and unbound naphthyridine nitrogen.