Selective Oxidation and Functionalization of 6-Diphenylphosphinoacenaphthyl-5-tellurenyl Species 6-Ph₂P-Ace-5-TeX (X = Mes, Cl, O₃SCF₃). Various Types of P–E···Te(II,IV) Bonding Situations (E = O, S, Se)

Abstract

The syntheses of the diaryltelluride 6-Ph 2 P(O)-Ace-5-TeMes (1O), the tellurenyl(II) chlorides 6-Ph 2 P(E)-Ace-5-TeCl (2O, E = O; 2S, E = S; 2Se, E = Se), the ditelluroxonium(IV) bis(triflate) [6-Ph 2 P(O)-Ace-5-TeO] 2 (O 3 SCF 3 ) 2 (3O), the diaryltellurium(IV) dichloride 6-Ph 2 P(O)-Ace-5-TeMesCl 2 (4O), the diarylhalotelluronium(IV) polyhalides [6-Ph 2 P(O)-Ace-5-TeMesBr]Br 3 (5O) and [6-Ph 2 P(O)-Ace-5-TeMesI] 2 I 8 (6O), and the aryltellurium(IV) trihalides 6-Ph 2 P(O)-Ace-5-TeX 3 (7O, X = Cl; 8O, X = Br; 9O, X = I) are reported. All compounds have been characterized experimentally by means of multinuclear NMR spectroscopy as well as single-crystal X-ray crystallography. The diverse P−E•••Te bonding situations (E = O, S, Se) in the peri region have also been investigated in detail by complementary DFT studies including the calculation of peri interaction energies (α-PIE) as well as topological analyses of the electron and pair densities according to the AIM and ELI-D space-partitioning schemes and evaluation of noncovalent bonding aspects applying the NCI index. To illustrate the different bond situations, appropriate Lewis formula representations have been suggested.

The Effect of Donor Additives on the Stability and Structure of 5‐Diphenylphosphinoacenaphth‐6‐yllithium

“…5‐Diphenylphosphinoacenaphth‐6‐yllithium, 5‐Ph 2 P‐Ace‐6‐Li, an important starting material for the synthesis of peri ‐substituted scaffolds was isolated for the first time and fully characterized as the tetranuclear (5‐Ph 2 P‐Ace‐6‐Li) 4 · 4toluene and as the dinuclear (5‐Ph 2 P‐Ace‐6‐Li · OEt 2 ) 2 · toluene by X‐ray crystallography and 7 Li MAS and 31 P MAS NMR spectroscopy. Apart from Et 2 O, other donor solvents/additives including THF, DME, TMEDA, DABCO give rise to rapid decomposition of 5‐Ph 2 P‐Ace‐6‐Li.…”

“…Ever since their discovery about 100 years ago, organolithium compounds rank amongst the most versatile and widely used reagents in organic and organometallic chemistry In this regard, 5‐diphenylphosphinoacenaphth‐6‐yllithium, 5‐Ph 2 P‐Ace‐6‐Li (Scheme ), has been extensively used for the preparation of peri ‐substituted acenaphthyl scaffolds to study the through‐space interactions between the P atom and a variety of main group elements (B, Al, Ga, In, Tl, Si,, Sn, Pb, P, As, Sb,, Bi and Te) as well as transition metals (Au,, Hg, ).…”

Synthesis and Reactivity of Bis(6‐diphenylphosphinoacenaphth‐5‐yl)ditelluride

“…Purging air through a solution of 1 provided the related bis(6‐diphosphinoxyacenaphth‐5‐yl)ditelluride, [6‐Ph 2 P(O)‐Ace‐5‐] 2 Te 2 ( 2 ) in 90 % yield (Scheme ). Alternatively, 2 was obtained by the reduction of (6‐diphenylphosphinoxy‐acenaphth‐5‐yl)tellurenyl chloride, 6‐Ph 2 P(O)‐Ace‐5‐TeCl with K‐selectride in 88 % yield (Scheme ). The ditellurides 1 and 2 were obtained as red and yellow crystals that are reasonably soluble in organic solvents such as toluene, THF, and CH 2 Cl 2 .…”

“…Dry solvents were collected with a SPS800 mBraun solvent system. (6‐(Diphenylphosphanyl)acenaphth‐5‐yl)tellurenyl chloride and [6‐Ph 2 PAce‐5‐Te]Cl, (6‐(diphenylphosphinoxy)acenaphth‐5‐yl)tellurenyl chloride, 6‐Ph 2 P(O)Ace‐5‐TeCl, were prepared according to literature procedures. 1 H‐, 13 C‐, 31 P‐ and 119 Te‐NMR spectra were recorded at room temperature with a Bruker Avance‐360 spectrometer and are referenced to tetramethylsilane ( 1 H, 13 C), phosphoric acid (85 % in water) ( 31 P), and dimethyltelluride( 125 Te).…”

“…Our work on peri ‐substituted acenaphthyltellurium compounds prompted us to prepare bis(6‐diphosphinoacenaphth‐5‐yl)ditelluride, (6‐Ph 2 P‐Ace‐5‐) 2 Te 2 ( 1 ), which is not assessable by the same route as it turned out to be sensitive towards molecular oxygen (Scheme ). Unlike the oxidation of II , the reaction of 1 with molecular oxygen occurred in the absence of UV light and afforded the related bis(6‐diphosphinoxyacenaphth‐5‐yl)ditelluride, [6‐Ph 2 P(O)‐Ace‐5‐] 2 Te 2 ( 2 ) without affecting the integrity of the Te–Te bond (Scheme ).…”