43395-B3
Boranes as Lewis Bases and the Synthesis of Metallaboratranes
The synthesis and reactivity of new poly(mercaptoimidazolyl)borate complexes continues to be explored while the quest for metallaboratrane complexes of cobalt, rhodium, iridium, and platinum –metals for which such species are known– remains elusive. The synthesis and characterization of the first BmR complexes of Cu(I), Ag(I), and Au(I), including phosphine and diphosphine derivatives, has been completed and will be published in due course. Similarly, the preparation of the first BmR compounds of indium and bismuth, including halide, dithiocarbamate and xanthate derivatives, and preliminary thermogravimetric analysis (TGA) studies suggesting they can be cleanly converted to the corresponding binary sulfides M2S3 (M = In, Bi) will be reported shortly. The synthesis of a new bis(mercaptoimidazolyl)methane ligand (BmmtBu) has been completed and a series of copper(I) derivatives, including (BmmtBu)CuX (X = Cl, Br, I) and (BmmtBu)Cu(PPh3)X (X = Cl, Br), has been attained. These complexes exhibit enhanced solubility relative to their BmmMe analogues and a manuscript describing the synthesis of methanobactin analogues based on these ligands is in preparation. This chemistry is also now being expanded to the preparation of a second generation of methanobactin analogues incorporating new bis(mercaptoimidazolyl)xylene (BmxR) ligands. The coordination chemistry of bis(thioether)silanes is another area of interest being pursued, and the synthesis of the first such ligands and their tin(IV) derivatives has been reported. The dithioether Me2Si(CH2SMe)2 (BtsMe) has also been used, in collaboration with Prof. Jeffrey J. Rack (Dept. of Chemistry, Ohio University), to study the femtosecond isomerization of a photochromic ruthenium(II) disulfoxide complex obtained in turn from [(bipy)2Ru(BtsMe)]2+.
