Structure and Reactivity of a Pyridine-1-imido-2-thiolato Complex of Iridium(III), Cp*Ir(1-N-2-Spy), Generated by Photolysis of the (Azido)(pyridine-2-thiolato) Complex, Cp*Ir(2-Spy)(N₃)

Abstract

Photolysis of the (azido)(pyridine-2-thiolato)iridium(III) complex CpIr(2-Spy)(N3) (1) gave a pyridine-1-imido-2-thiolato complex, CpIr(1-N-2-Spy) (2), in which one of the nitrogen atoms of the azide ligand has been inserted into the Ir-N(py) bond (Cp = eta5-C5Me5). Complex 2 reacted quantitatively with methyl iodide to give the N-methylated product, [CpIr(1-NMe-2-Spy)]I (3). X-ray crystallography revealed that both 2 and 3 have similar two-legged piano stool structures with planar 1-N-2-Spy2- or 1-NMe-2-Spy- ligands, which form iridacyclopentadienyl-like rings by moderate S(ppi)/N(ppi) to Ir(dpi) pi donation.

Terminal Nitrido and Imido Complexes of the Late Transition Metals

“…Chelating imido species will not be discussed. [27][28][29][30] The last section will focus on species that have been postulated in the organic chemistry literature, but do not have any stable analogs that have been characterized. Some of these last species are highly speculative, and open up interesting opportunities as targets for synthetic efforts.…”

Reactions of half-sandwich Co(III) complexes with heterocyclic thione ligands: η2-N, S coordination mode and formation of S–S bond

“…There are two or more donor atoms in these types of ligands, which endows them with multifunctional coordination ability. A heterocyclic thionate ligand can coordinate to one metal center as a monodentate or bidentate ligand, and can also act in polynuclear complexes as a bridging ligand between two, three, or even more metal centers [10][11][12][13][14].…”

“…Although a lot of complexes of such heterocyclic thione ligand with metal atoms have been synthesized and studied [15][16][17][18][19][20][21], the half-sandwich complexes, which have cobalt, rhodium, and iridium centers with these ligands, are still under comprehensive investigation [22][23][24]. In our previous work, we synthesized complex Cp * CoI(2-PyS) in a very high yield, which was used as a starting material to study the reaction with monodentate or bidentate 1,2-dicarba-closo-dodecaborane thiolate, 2-pyridinethiolate, 2-pyridinethione, 4-pyridinethiolate and benzenethiolate ligands and some interesting phenomena were detected, such as C-H activation reaction [25,26] (2) or Cp * CoI(2-TaS) (3) was isolated as green crystals in about 80% yield, respectively (Scheme 1).…”

Reactions of 2-pyridinethiolate cobalt(III) complexes with pyridinethiolate or benzenethiolate ligands

“…There are two donor atoms in these types of ligands, a sulfur atom and a nitrogen atom, which are considered as a soft center and a hard center, respectively [5,6], enabling these ligands to coordinate to both soft and hard metals. 2-Pyridinethiolates ligands interact with metal atoms in several ways, which may be coordinated as a monodentate group through the sulfur or nitrogen atom, as a bidentate chelating moiety through the sulfur and nitrogen donors, or as a bridging ligand through both donor groups [7][8][9][10][11][12][13].…”