Crystal structure of 2,2,4,4-tetrahydro-2,2,2,4,4,4-hexaphenyl-1,3,2,4-dioxadistibetane (triphenylstibene oxide dimer) and related compounds

Triphenylantimony(V) o‐amidophenolates with unsymmetrical N‐aryl group for a reversible dioxygen binding

“…The peroxo-bonds O-O in symmetrical complexes are the same [1.461(3) Å in spiroendoperoxide of (AP-iPr,iPr)SbPh 3 and 1.466(2) in spiroendoperoxide of (APMe,Me)SbPh 3 ], [7,8b] and endoperoxide 3,3-dihidro-5,5-dimethyl-3,3,3-triphenyl-1,2,4,3-trioxastibolane has an O-O distance of 1.468 Å. [11] The interaction of dioxygen with transition metal complexes is well known. [12] Some of o-iminosemiquinonato/oamidophenolato transition metal complexes were also shown to react with molecular oxygen to form different derivatives.…”

Well‐Defined Stibonic and Tellurinic Acids

“…Aggregation was also observed for related triarylantimony oxides and diaryltellurium oxides, which exist in two distinctively different structures, namely as asymmetric dimers, for example (Ph 3 SbO) 2 [6] and (Ph 2 TeO) 2 , [7] and as one-dimensional polymers, for example, (Ph 3 SbO) n [8] and (pAns 2 TeO) n (Ans = MeOC 6 H 4 ). [9] These observations prompted us to study the structures of archetypal stibonic and tellurinic acids that are kinetically stabilized by a bulky m-terphenyl substituent.…”

“…[12] In 3 the equatorial and axial endocyclic Sb À O bond lengths (1.913(2) and 2.035(2) ) vary only marginally (by 0.122(2) ) and compare well with those of (Ph 3 SbO) 2 (1.928(3) and 2.071(4) ). [6] By contrast, in 6 the equatorial and axial endocyclic TeÀO bond lengths (1.897 (5) and 2.143(5) ) differ by 0.246(5) . In the related compound (Ph 2 TeO) 2 , the difference between the equatorial and axial TeÀO bonds (av 1.89(1) and 2.55(1) ) of 0.66(1) is even more pronounced.…”

Catalytic Action of Triarylstibanes: Oxidation of Benzoins into Benzyls Using Triarylstibanes Under an Aerobic Condition

“…It can be assumed that the excessive exposure of 2a to oxygen may give rise to inactive Ph 3 Sb-oxo species for the oxidation of 1a; hence the inactive species could not revert to 2a. [33][34][35][36][37][38] These results imply that the oxidation of 1a into 3a should be induced by a certain oxidant such as triphenylstibane oxide (Ph 3 SbO) generated from the antimony reagent and oxygen. In fact, the reaction of 1a with catalytic amount of Ph 3 SbO brought about the same oxidation to afford 3a in high yield.…”

“…The initial step of this reaction should involve the oxidation of 2a into SbPh 3 -oxo species (oxide) with aerobic oxygen, although the structure of the oxide could not be specified at present. [33][34][35][36][37][38] The formation of the oxide may be assisted by the formation of Ph 3 Sb-benzoin complex A caused by Sb · · · O aggregation with non-bonding interaction, 39,40) because prolonged contact (Ͼ48 h) of 2a with air or oxygen without benzoin did not form any oxides and all of the stibane was recovered unchanged. The electron-attracting group on antimony reagents may facilitate the aggregation of Ar 3 Sb with benzoin and enhance the formation of the active oxide for the oxidation: the steps Ar 3 Sb →A→B→(Ar 3 SbO) n in Chart 2.…”