0000000000136870
AUTHOR
Jamie Ritch
An Unusual Ditelluride: Synthesis and Molecular and Electronic Structures of the Dimer of the Tellurium-Centered Radical [TePiPr2NiPr2PTe]•
Facile formation of the ditelluride [(TePiPr2NiPr2PTe-)2], which exists as a centrosymmetric dimer (see picture: Te green, P purple, N blue, C gray) with a weak Te[BOND]Te bond, embodies a new feature of the chemistry of dichalcogenoimidodiphosphinate ligands. The monotelluride HPiPr2NiPr2PTe analogue is obtained as the P[BOND]H tautomer. peerReviewed
New Insights into the Chemistry of Imidodiphosphinates from Investigations of Tellurium-Centered Systems
Dichalcogenido-imidodiphosphinates, [N(PR2E)2]− (R = alkyl, aryl), are chelating ligands that readily form cyclic complexes with main group metals, transition metals, lanthanides, and actinides. Since their discovery in the early 1960s, researchers have studied the structural chemistry of the resulting metal complexes (where E = O, S, Se) extensively and identified a variety of potential applications, including as NMR shift reagents, luminescent complexes in photonic devices, or single-source precursors for metal sulfides or selenides. In 2002, a suitable synthesis of the tellurium analogs [N(PR2Te)2]− was developed. In this Account, we describe comprehensive investigations of the chemistry…
Experimental and Theoretical Investigations of Structural Isomers of Dichalcogenoimidodiphosphinate Dimers: Dichalcogenides or Spirocyclic Contact Ion Pairs?
A synthetic protocol for the tert-butyl-substituted dichalcogenoimidodiphosphinates [Na(tmeda){(EPtBu2)2N}] (3 a, E=S; 3 b, E=Se; 3 c, E=Te) has been developed. The one-electron oxidation of the sodium complexes [Na(tmeda){(EPR2)2N}] with iodine produces a series of neutral dimers (EPR2NPR2E[BOND])2 (4 b, E=Se, R=iPr; 4 c, E=Te, R=iPr; 5 a, E=S, R=tBu; 5 b, E=Se, R=tBu; 5 c, E=Te, R=tBu). Attempts to prepare 4 a (E=S, R=iPr) in a similar manner produced a mixture including HN(SPiPr2). Compounds 4 b, 4 c and 5 a–c were characterised by multinuclear NMR spectra and by X-ray crystallography, which revealed two alternative structures for these dimeric molecules. The derivatives 4 b, 4 c, 5 a an…
New tellurium-containing ring systems
The recent discovery of a suitable synthesis of the monoanionic ditelluroimidodiphosphinate ligands [TePR2NPR2Te]− (R = Ph, iPr, tBu) has facilitated investigations of the fundamental chemistry of these chelating inorganic ligands. This article is focused on aspects of that chemistry in which the behaviour of this ditelluro PNP ligand differs from that of the well-studied dithio and diseleno congeners. The emphasis is on new tellurium-containing ring systems formed in: (a) redox transformations and (b) the synthesis of metal complexes. peerReviewed