Experimental and Computational Investigations of Platinum Complexes of Selenium Diimide and Some Novel Selenium-Nitrogen Ligands

The reaction of selenium diimide Se[N(t-Bu)]2 and PtCl2 afforded an N,N’-chelated complex [PtCl2{N,N’-Se[N(t-Bu)]2}] (1) in good yield and [PtCl2{N,N’-SeO[NH(t-Bu)]2}] (2) as a minor product. Attempts to prepare 2 by direct reaction of SeOCl2 with Li[NH(t-Bu)] in toluene followed by addition of PtCl2 produced cyclic Se4[N(t-Bu)]4 in solution (77Se NMR spectrum) and a small amount of the complex [PtCl3{Se,Se’,Se”-Se4[N(t-Bu)]4}][Pt2Cl5{Se,Se’,Se”-Se3[N(t-Bu)]2}]∙3MeCN (3∙3MeCN), which contains tridentate Se4[N(t-Bu)]4 in the cation and the novel, acyclic bridging ligand [SeN(t-Bu)SeN(t-Bu)Se]2- in the anion. The reaction of Se[N(t-Bu)]2 with [PtCl2(NCPh)2] in THF produced the dinuclear complex [Pt2Cl6{SeN(t-Bu)C(Ph)NH}2]∙2C4H8O (4∙2THF) as the major product and only a few crystals of 1. The possible formation of SeO[NH(t-Bu)]2 or 2 by the reaction of Se[N(t-Bu)]2 or 1, respectively, with adventitious water and the pathway for the production of 4 were investigated through revPBE GGA/def2-TZVP calculations. The X-ray structures of 1, 2, 3∙3MeCN, and 4∙2THF have been determined.The accepted manuscript in pdf format is listed with the files at the bottom of this page. The presentation of the authors' names and (or) special characters in the title of the manuscript may differ slightly between what is listed on this page and what is listed in the pdf file of the accepted manuscript; that in the pdf file of the accepted manuscript is what was submitted by the author