title: Selective formation of heteroligated Pt(II) complexes with bidentate phosphine-thioether (P,S) and phosphine-Selenoether (P,Se) ligands via the halide-induced ligand rearrangement reaction.
abstract: Bidentate phosphine-selenoether (P,Se) ligands were synthesized, and their heteroligated Pt(II) complexes were made and studied. The unique "P,S/P,Se" ligand coordination to Pt(II) can be realized via the halide-induced ligand rearrangement reaction. In all cases, the exclusive formation of semi-open heteroligated complexes was achieved as shown by (31)P and (77)Se NMR spectroscopy and from single crystal X-ray diffraction studies. This is the first example of the use of (77)Se NMR spectroscopy to characterize these types of structures through direct observation of the weak-link interaction with the metal center. Heteroligated structure formation is believed to be driven by the relative electron-donating ability of the substituent groups on the seleno or thioether moieties. This effect is studied by comparing the structures of corresponding "P,SMe" and "P,SeMe" complexes bearing a hemilabile "P,SCH(2)CF(3)" group, which is less sterically demanding than "P,SPh" but is similar in terms of electron withdrawing ability.
authors.affiliation: Department of Chemistry and the International Institute for Nanotechnology, Northwestern University, 2145 Sheridan Road, Evanston, Illinois 60208, USA.
authors.forename: Alexander M
authors.initials: AM
authors.lastname: Spokoyny
authors.forename: Mari S
authors.initials: MS
authors.lastname: Rosen
authors.forename: Pirmin A
authors.initials: PA
authors.lastname: Ulmann
authors.forename: Charlotte
authors.initials: C
authors.lastname: Stern
authors.forename: Chad A
authors.initials: CA
authors.lastname: Mirkin