Synthesis Structures and Properties of Ruthenium Piano Stool Complexes

Abstract

This research investigated the synthesis of a series of new C3v RuII complexes with pyridine or pyridyl ligands. Commercial ruthenium chloride dimers ([Ru(Bz)Cl2]2, [Ru(Cym)Cl2]2, [Ru(HMB)Cl2]2) were initially used to synthesise the important precursors [Ru(Bz)(N2H4)3][BPh4]2 (1), [Ru(Cym)(N2H4)3][BPh4]2 (6) and [Ru(HMB)(N2H4)3][BPh4]2 (12), which was followed by the synthesis of a series of Ruthenium tris-pyridyl complexes that included [Ru(Cym)(ein)3][BPh4]2 (9). Investigations into different purification methods, which included recrystallisation in different solvent combination systems, alumina column and sephadex column revealed that the most efficient method for a silica column was eluant DCM:acetone(dry)= 95:5 or DCM:acetonitrile (dry)= 95:5. A range of novel compounds was successfully made. Complexes [Ru(Bz)(N2H4)3][BPh4]2 (1), [Ru(Bz)(py)3][BPh4]2 (2), [Ru(Cym)(N2H4)3][BPh4]2 (6), [Ru(Cym)(py)3][BPh4]2 (7), [Ru(Cym)(pic)3][BPh4]2 (8) were all known compounds. Compounds [Ru(Bz)(pic)3][BPh4]2 (3), [Ru(Bz)(ein)3][BPh4]2 (4), [Ru(Bz)(ppy)3][BPh4]2 (5), [Ru(Cym)(ein)3][BPh4]2 (9), [Ru(Cym)(ppy)3][BPh4]2 (10), [Ru(HMB)(N2H4)3][BPh4]2 (12), [Ru(HMB)(py)3][Cl]2 (13), [Ru(HMB)(pic)3][Cl]2 (14), [Ru(HMB)(ein)3][Cl]2 (15) and [Ru(HMB)(ppy)3][BPh4]2 (16) are all new complexes. The compounds (1-10) were fully characterised by electronic spectroscopy and electrochemical methods. Eight crystal structures of [Ru(Bz)(N2H4)3][BPh4]2 (1), [Ru(Bz)(py)3][BPh4]2 (2), [Ru(Cym)(N2H4)3][BPh4]2 (6), [Ru(py)3(DMF)3][BPh4]2 (11), [Ru(HMB)(N2H4)3][BPh4]2 (12), [Ru(HMB)(py)(Cl)2] (17), [Ru(HMB)(pic)(Cl)2] (18) and [Ru(HMB)(pic)(Cl)2]•CH2Cl2 (19) were obtained as well.

Date of Award	1 Aug 2017
Original language	English
Awarding Institution	The University of Manchester
Supervisor	Benjamin Coe (Supervisor) & Mark Whiteley (Supervisor)