Date of Award
Open Access Thesis
Chemistry and Biochemistry
College of Arts and Sciences
Dmitry V. Peryshkov
The reaction of coordination compounds of palladium, rhodium, ruthenium and nickel with thiolated ortho-carborane derivatives- 1,2-dimercapto-o-carborane (1,2-(HS)2-1,2- C2B10H10 ) and 9,12- dimercapto-o-carborane (9,12-(HS)2-1,2- C2B10H10 ) and with carbornanyl dicarboxylate has been studied. To further investigate the chemistry of o-carboranyl dithiolate, both of the reported literature dithiols have been employed to study the reactivity with some of the above mentioned transition metal coordination compounds. The 1,2-dimercapto-o-carborane reacts with bis(triphenylphosphine)palladium(II) chloride [PdCl2(PPh3)2] to form a square planar bis(triphenylphosphine)palladium(II) carboranyl dithiolate (PdC2B10S2(PPh3)2) complex. With the inspiration from the reactivity of the dithiols and versatility of carboranyldithiolate ligand in organometallic chemistry, new avenue of carboranyltetrathiolate coordination could be envisioned. The synthesis of 1,2,9,12- tetramercapto- ortho-Carborane has also been attempted.
Extremely sterically demanding m-terphenyl amines are excellent ligands because of the ease in forming main group complexes in low coordination numbers but also provide a large area to study the reactivity between their nitrogen atom containing steric pocket and transition metal. Two well-known literature routes for the synthesis of m-terphenyl aniline has thoroughly been discussed within this paper in chapter 2. Additionally, terephenyl iodide (2’-iodo-3,3”,5,5”-tetramethyl-1,1’,3’,1”-terphenyl) has been synthesized following one of the reported synthetic route (Scheme 2.2, route A) and has paved a future foundation for our anticipated cyclization of the m-terphenyl aniline via borylation. Several attempts to synthesize m-terphenyl aniline has also been discussed within this paper as well.
Karki, S. B.(2016). Synthesis Attempts And Plausible Applications Of Dithiolated Ortho –Carboranyl Transition Metal Complexes And Synthesis Of Bulky Terphenyls. (Master's thesis). Retrieved from https://scholarcommons.sc.edu/etd/3861