Synthesis, characterization, and alkoxide transfer reactivity of dimeric Tl 2 (OR) 2 complexes

• Published in: Dalton transactions : an international journal of inorganic chemistry 2021-02, Vol.50 (7), p.2501-2509
• Main Authors: Grass, Amanda, Kulathungage, Lakshani Wathsala, Wannipurage, Duleeka, Yousif, Maryam, Ward, Cassandra L, Groysman, Stanislav
• Format: Article
• Language: English
• ISSN: 1477-9226; 1477-9234
• DOI: 10.1039/d0dt03917a

Reaction of LiOC Bu Ph with TlPF forms the dimeric Tl (OC Bu Ph) complex, a rare example of a homoleptic thallium alkoxide complex demonstrating formally two-coordinate metal centers. Characterization of Tl (OC Bu Ph) by H and C NMR spectroscopy and X-ray crystallography reveals the presence of two isomers differing by the mutual conformation of the alkoxide ligands, and by the planarity of the central Tl-O-Tl-O plane. Tl (OC Bu Ph) serves as a convenient precursor to the formation of old and new [M(OC Bu Ph) ] complexes (M = Cr, Fe, Cu, Zn), including a rare example of T-shaped Zn(OC Bu Ph) (THF) complex, which could not be previously synthesized using more conventional LiOR/HOR precursors. The reaction of [Ru(cymene)Cl ] with Tl (OC Bu Ph) results in the formation of a ruthenium(ii) alkoxide complex. For ruthenium, the initial coordination of the alkoxide triggers C-H activation at the ortho-H of [OC Bu Ph] which results in its bidentate coordination. In addition to Tl (OC Bu Ph) , related Tl (OC Bu (3,5-Me C H )) was also synthesized, characterized, and shown to exhibit similar reactivity with iron and ruthenium precursors. Synthetic, structural, and spectroscopic characterizations are presented.