0000000000457190
AUTHOR
Jason Dutton
Electronic Structures of Main-Group Carbene Analogues
The electronic structures of 15 group 13−16 carbene analogues are analyzed using various quantum chemical methods and compared to the data obtained for the parent N-heterocyclic carbene (NHC), imidazol-2-ylidene. The results of this study present a uniform analysis of the similarities and differences in the electronic structures of p-block main-group carbene analogues. Though all systems are formally isovalent, the theoretical analyses unambiguously indicate that their electronic structures run the gamut from CC localized (group 13) to CN localized (group 16) via intermediate, more delocalized, systems. In particular, neither the stibenium ion nor any of the chalcogenium dications is a dire…
Extending the Series: Synthesis and Characterization of a Dicationic N-Heterocyclic Selenium Carbene Analogue
The room-temperature reaction between the Dipp2DAB ligand, SnCl2, and SeCl4 results in the quantitative formation of a dicationic N-heterocyclic “carbenoid”. This represents the first example of a chalcogenium dication that mimics the ubiquitous Arduengo-type carbenes; however, the electronic structure is significantly different. peerReviewed
Tellurium(II)-Centered Dications from the Pseudohalide “Te(OTf)2”
Te for two: Supported by pyridine- or carbene-based ligands, tellurium-centered dications are prepared in high yield and include a dicationic tellurium analogue of the recently synthesized “carbodicarbene”. The key to accessing these compounds is the isolation of a base-stabilized form of TeOTf2 (see structure), a new highly electrophilic reagent for tellurium chemistry. peerReviewed
Homoleptic Pnictogen-Chalcogen Coordination Complexes
The synthesis and structural characterization of dicationic selenium and tellurium analogues of the carbodiphosphorane and triphosphenium families of compounds are reported. These complexes, [Ch(dppe)][OTf]2 [Ch = Se, Te; dppe = 1,2-bis(diphenylphosphino)ethane; OTf = trifluoromethanesulfonate], are formed using [Ch]2+ reagents via a ligand-exchange protocol and represent extremely rare examples of homoleptic pnictogen → chalcogen coordination complexes. The corresponding arsenic compounds were also prepared, [Ch(dpAse)][OTf]2 [Ch = Se, Te; dpAse = 1,2-bis(diphenylarsino)ethane], exhibiting the first instance of an arsenic → chalcogen dative bond. The electronic structures of these unique c…