Reactivity of Organotin(I) Dimers RSnSnR (R = 2,6-(Me₂NCH₂)₂C₆H₃, 4-t-Bu-2,6-{P(O)(O-i-Pr)₂}₂C₆H₂) with Diaryl Dichalcogenides, ArEEAr (E = S, Se, Te; Ar = Ph, 2-C₅H₄N): Control of Secondary Sn···Sn Interactions by Intramolecular Coordination and Identity of the Aryl Chalcogenate

Abstract

The reactions of the in situ prepared organotin(I) compounds RSnSnR with diaryl dichalcogenides ArEEAr provided, depending on the ratio of the reactants, the intramolecularly coordinated heteroleptic organotin(II) chalcogenoarylates RSnEAr

Oxidative Addition of Disulfides, Alkyl Sulfides, and Diphosphides to an Aluminum(I) Center

“…This reactivity is consistent with the activation of disulfides with other low-valent main-group species such as silylenes, germylenes, stannylenes, ,, and plumbylenes as well as low-valent antimony and bismuth complexes . FLPs have also effected the cleavage of the S–S bond in disulfides .…”

Oxidative Addition and Reductive Elimination at Main-Group Element Centers

“…Jambor and Jurkschat extended their work on pincer-supported distannynes (or distannylenes) to include the oxidative addition of dichalcogenides ArE–EAr (E = S, Se, Te) to the Sn­(I) compound 437 . , These reactions proceeded with E–E bond cleavage and gave Sn­(II) chalcogenides while the Sn­(II) sulfide and selenide can be oxidized further to the corresponding Sn­(IV) trichalcogenides (Scheme ). A similar reactivity was also observed with the OCO pincer ligated distannynes; however, the second oxidative addition of ArSe–SeAr does not occur even upon heating to 120 °C in THF …”

Tin and Lead Phosphanido Complexes: Reactivity with Chalcogens

“…The crystal structure of 4-Sn-Cy-Se 2 (Figure and Table for selected bond lengths and angles) is similar to that of the germanium analogue, with η 1 binding of the phosphinodiselenoate ligand to tin, an exo conformation of the phosphinodiselenoate ligand to the β-diketiminato tin metallocycle, and an acute Sn–Se–P bond angle (95.14°). The Sn–Se1 bond length of 2.6549(5) Å is similar those in other Sn–Se single bonds. − The P–Se1 single bond [2.2194(11) Å] is shorter than the P–Se bond of 2-Sn-Cy-Se but longer than the PSe2 double bond [2.1197(11) Å]. Although the Sn···Se2 distance of 3.508 Å is smaller than the sum of the van der Waals radii for tin and selenium (4.07 Å), the distance is much longer than that of a typical Sn–Se bond (2.55–2.60 Å), − indicating that there is, at most, only a weak interaction.…”

“…The Sn–Se1 bond length of 2.6549(5) Å is similar those in other Sn–Se single bonds. − The P–Se1 single bond [2.2194(11) Å] is shorter than the P–Se bond of 2-Sn-Cy-Se but longer than the PSe2 double bond [2.1197(11) Å]. Although the Sn···Se2 distance of 3.508 Å is smaller than the sum of the van der Waals radii for tin and selenium (4.07 Å), the distance is much longer than that of a typical Sn–Se bond (2.55–2.60 Å), − indicating that there is, at most, only a weak interaction.…”

“…In the solid state, 2-Sn-Cy-Se is isostructural with the germanium analogue, with a rare κ-Se binding mode for the phosphinoselenoite ligand (Figure and Table for selected bond lengths and angles). , The Sn–Se bond length of 2.6059(3) Å is within the range reported for Sn–Se single bonds (2.55–2.68 Å) − and longer than that reported for SnSe double bonds (2.25–2.39 Å). − The Se–P bond length of 2.2584(6) Å is similar to that of the germanium analogue [2.2602(9) Å], with the Sn–Se–P bond angle [91.388(17)°] more acute than the Ge–Se–P angle system [94.07(3)°].…”