Spirocyclic, macrocyclic and ladder complexes of coinage metals and mercury with dichalcogeno P2N2-supported anions.

Metathetical reactions of alkali-metal derivatives of the dianion [(t)BuN(Se)P(µ-N(t)Bu)2P(Se)N(t)Bu](2-) ((2Se2-)) with Ag(NHC)Cl, Ag[BF4], AuCl(THT) and HgCl2, as well as the reaction of 2S(2-) with AuCl(THT) were investigated. The observed products all incorporate the monoprotonated ligands 2SeH(-) or 2SH(-) in a variety of structural arrangements around the metal centres, including tetrameric and trimeric macrocycles [Ag and Au (E = Se)], a ladder (Au, E = S) and a spirocycle (Hg); the ladder contains both the dianion 2S(2-) and the monoanion 2SH(-) as ligands linking three Au2 units. All complexes have been characterised in the solid state by single crystal X-ray analyses and in solution by multinuclear ((1)H, (31)P and (77)Se) NMR spectra.

Main group tellurium heterocycles anchored by a P(2)(V)N(2) scaffold and their sulfur/selenium analogues.

A comprehensive investigation of reactions of alkali-metal derivatives of the ditelluro dianion [TePV(NtBu)(µ-NtBu)]22­ (L2­, E = Te) with p-block element halides produced a series of novel heterocycles incorporating P2VN2 rings, tellurium, and group 13­16 elements. The dianion engages in Te,Te'-chelation to the metal center in Ph2Ge and R2Sn (R = tBu, nBu, Ph) derivatives; similar behavior was noted for group 14 derivatives of L2­ (E = S, Se). In the case of group 13 trihalides MCl3 (M = Ga, In), neutral spirocyclic complexes (L)M[NtBu(Te)PV(µ-NtBu)2PIIIN(H)tBu)] (M = Ga, In) comprised of a Te,Te'-chelated ligand L2­ and a N,Te-bonded ligand resulting from loss of Te and monoprotonation were obtained. In reactions with RPCl2 (R = tBu, Ad, iPr2N) a significant difference was observed between Se- and S-containing systems. In the former case, Se,Se'-chelated derivatives were formed in high yields, whereas the N,S-chelated isomers predominated for sulfur. All complexes were characterized by multinuclear (1H, 31P, 77Se, 119Sn, and 125Te) NMR spectroscopy; this technique was especially useful in the analysis of the mixture of (L)(Se) and (L)(SeSe) obtained from the reaction of Se2Cl2 with L2­ (E = Te). Single-crystal X-ray structures were obtained for the spirocyclic In complex (9), (L)GePh2 (E = Te, 10), (L)SntBu2 (E = Te, 12a); E = Se, 12aSe, E = S, 12aS) and (L)(µ-SeSe) (E = Te, 16).

Peri-substituted phosphorus-tellurium systems-an experimental and theoretical investigation of the P···Te through-space interaction.

A series of peri-substituted phosphorus-tellurium systems R'Te-Acenap-PR2 (R' = Ph, p-An, Nap, Mes, Tip; Acenap = acenaphthene-5,6-diyl (-C12H8); R = (i)Pr, Ph) exhibiting large "through-space" spin-spin coupling constants and the "onset" of three-center four-electron type interactions is presented. The influence of the substituents at the phosphorus and tellurium atoms as well as their behavior upon oxidation (with S, Se) or metal-coordination (Pt, Au) is discussed using NMR spectroscopy, single-crystal X-ray diffraction, and advanced density functional theory studies including NBO, AIM, and ELI-D analyses.

Sodium and rhodium complexes of a spirocyclic Te5 dianion supported by P2N2 rings.

Reactions of the dianion [Te((t)BuN)P(µ-N(t)Bu)2P(N(t)Bu)Te](2-) with I2 or [Cp*RhCl2]2 unexpectedly produced complexes of the novel spirocyclic Te5 dianion [{(t)BuN(Te)P(µ-N(t)Bu)2P(Te)N(t)Bu}2µ-Te](2-), which is N,N'-coordinated to two Na(+) ions in the disodium derivative and adopts a Te,Te',Te''-bonding mode in the Cp*Rh complex.

The activation of Woollins' reagent. Isolation of pyridine stabilised PhPSe2.

Woollins' reagent (WR, (PhPSe2)2) plays an essential role in the selenation of organic compounds. Reaction of WR with pyridine gives the P(V) species PhPSe2 stabilised by pyridine coordination which is the first crystallographically characterised mononuclear RPSe2 system stabilised by an external molecule and has potential as a selenation reagent for reactions under mild conditions.

Isolatable organophosphorus(III)-tellurium heterocycles.

A new structural arrangement Te3 (RP(III) )3 and the first crystal structures of organophosphorus(III)-tellurium heterocycles are presented. The heterocycles can be stabilized and structurally characterized by the appropriate choice of substituents in Tem (P(III) R)n (m=1: n=2, R=OMes* (Mes*=supermesityl or 2,4,6-tri-tert-butylphenyl); n=3, R=adamantyl (Ad); n=4, R=ferrocene (Fc); m=n=3: R=trityl (Trt), Mesor by the installation of a P(V) 2 N2 anchor in RP(III) [TeP(V) (tBuN)(µ-NtBu)]2 (R=Ad, tBu).

A planar dianionic ditelluride and a cyclic tritelluride supported by P2N2 rings.

Oxidation of alkali metal derivatives of [Te((t)BuN)P(µ-N(t)Bu)(2)P(N(t)Bu)Te](2-) with I(2) produces the intermediate ditelluride dianion [Te((t)BuN)P(µ-N(t)Bu)(2)P(N(t)Bu)Te](2)(2-) with a planar PTeTeP conformation and, subsequently, the cyclic tritelluride [((t)BuN)P(µ-N(t)Bu)(2)P(N(t)Bu)(µ-TeTeTe)].

Planar P(6)E(6) (E = Se, S) macrocycles incorporating P(2)N(2) scaffolds.

Oxidation of alkali metal derivatives of the dianions [E((t)BuN)P(µ-N(t)Bu)(2)P(N(t)Bu)E](2-) (E = S, Se) with I(2) produces 15-membered macrocycles in which a planar P(6)E(6) motif is stabilised by perpendicular P(2)N(2) scaffolds.