3,4-Bis(1-adamantyl)-1,2-dithiete: the First Structurally Characterized Dithiete Unsupported by a Ring or Benzenoid Frame

Abstract

The structure determination of 3,4-bis(1-adamantyl)-1,2-dithiete, (C10H15)2C2S2 or C22H30S2, reported herein is the first crystallographic characterization of a 1,2-dithiete molecule unsupported by a benzenoid frame. Two independent molecules exist in the asymmetric unit separated by a pseudo-inversion center. The S2C2 four-membered dithiete ring is planar, with a trapezoidal shape enforced by the longer disulfide bond [average 2.086 (2) A] compared with the olefinic bond [average 1.363 (6) A]. The adamantyl substituents differ from one another by adopting slightly different rotational conformations with respect to the dithiete ring. The quaternary C atoms of the adamantyl groups deviate only slightly from the plane of the dithiete ring (average displacement of 0.023 A).

Sterically Hindered o‐Quinone Annulated with Dithiete: A Molecule Comprising Diolate and Dithiolate Coordination Sites

“…The bond lengths for SS, CS as well as sp 2 geometry of C4 and C5 atoms unambiguously correspond to dithiete structure for 2 and are closely comparable to those found in similar molecules 15. 16, 17…”

“…The bond lengths for S À S, C À S as well as sp 2 geometry of C4 and C5 atoms unambiguously correspond to dithiete structure for 2 and are closely comparable to those found in similar molecules. [15,16,17] To the best of our knowledge only one example of the isolation of stable benzoA C H T U N G T R E N N U N G [1, 2]dithiete has been described before. [16,17] BenzoA C H T U N G T R E N N U N G [1,2]dithiete was obtained as yellow crystals by photolysis of the corresponding dithiin.…”

“…To the best of our knowledge only one example of the isolation of stable benzo[1, 2]dithiete has been described before 16. 17 Benzo[1,2]dithiete was obtained as yellow crystals by photolysis of the corresponding dithiin.…”

Large Ligand Folding Distortion in an Oxomolybdenum Donor–Acceptor Complex

“…The superscripts a′ and a″ reflect the orbital symmetry with respect to a mirror plane that is oriented perpendicular to the dithiolene ring plane and bisecting both the S-S vector and the C=C bond. Removal of two electrons from the ϕ ip a ′ orbital of the dianionic dithiolene leads to the dithiete resonance form 33 , while removal of two electrons from the ϕ op a ′ orbital results in the dithione resonance form (Figure 3 right and Scheme 1). Since the ϕ ip a ″ orbital can form σ bonds with the metal d(xy) orbital, removal of two electrons from ϕ ip a ″ results in a ligand that is a very poor donor to the metal.…”

Radical CpNi(dithiolene) and CpNi(diselenolene) complexes: Synthetic routes and molecular properties

“…When the R groups are bulky (R = t-butyl or 1-adamantyl), the equilibrium between both species has been identified [29]. The molecular structure of 3,4-bis(1-adamantyl)-1,2-dithiete has been reported by Holm and co-workers [30]. Anyway, the 1,2-dithiete and 1,2-dithioketone forms show the same reactivities with low-valent metal sources, and then dithiolene complexes of higher valent metal can be obtained [24].…”