Synthesis of 2,6-bis(bis(2-(methylthio)phenyl)phosphino)-4-methylphenol, a novel polydentate ligand containing two tripodal [S,S,P,O] coordination pockets; crystal structure of the dimeric thallium(I) complex

Document Type

Article

Publication Date

8-2006

Department

Department of Chemistry

Abstract

The reactions of bis(2-(methylthio)phenyl)chlorophosphine (5a) (2 equivalents) with the O-protected 2,6-dilithio-4-methylphenol followed by acidic workup led to the isolation of 2,6-bis(bis(2-(methylthio)phenyl)phosphino)-4-methylphenol (2). Analogous reactions do not proceed if the sterically bulkier bis(2-(tert-butylthio)phenyl)chlorophosphine (5b) is used instead of 5a. Compound 2 is a topological analog of binucleading ligands built on a 2,6-diaminophenol core, where two tripodal N- or O-ligating compartments are flanking the phenolate functionality. A distinguishing feature of 2 is the “soft” donor environment of the potentially [S,S,P]-ligating pockets flanking the phenolic OH group. Reaction of 2 with TlOEt lead to the formation of the dimeric thallium(I) phenoxide (3), which was characterized by a single crystal X-ray diffraction study. In addition to μ-phenoxide ligation, in the solid state each thallium atom also interacts with two phosphorus atoms from the opposing ligands. The interactions are not equivalent, with the two TlI–P distances differing by ca. 0.3Å. No significant Tl···S interactions are present in the solid state. Room temperature 31P NMR measurements indicate the dynamic behavior of 3 in solution.

Publication Title

Zeitschrift fur Anorganische und Allgemeine Chemie

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