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

Autor:	Chad A. Mirkin, Charlotte L. Stern, Mari S. Rosen, Pirmin A. Ulmann, Alexander M. Spokoyny
Rok vydání:	2010
Předmět:	Denticity Chemistry Stereochemistry Ligand Substituent Nuclear magnetic resonance spectroscopy Medicinal chemistry Inorganic Chemistry chemistry.chemical_compound Thioether Polar effect Rearrangement reaction Physical and Theoretical Chemistry Phosphine
Zdroj:	Inorganic Chemistry. 49:1577-1586
ISSN:	1520-510X 0020-1669
DOI:	10.1021/ic901991w
Popis:	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.
Databáze:	OpenAIRE
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