Regioselective synthesis, X-ray structure, and reactivity of a tricyclic tetrasulfone, 1,3,5,7-tetramethyl-2,4,6,8,9,10-hexathiatricyclo[3.3.1.13,7]decane 2,2,4,4,6,6,8,8-octaoxide, derived from tetramethylhexathiaadamantane †

Miller, Glen P.; Jeon, Ingyu; Faix, A. Nikki; Jasinski, Jerry P.; Athans, Andreas J.; Tetreau, Mark C.

doi:10.1039/b004911p

Cited by 10 publications

(3 citation statements)

References 10 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The singlet C-S bond length (1.780 A ˚) is longer than that in the triplet state (1.753 A ˚) and is close to typical C-S single bond (1.79-1.82 A ˚). 26 In addition, the singlet C-N bond length (1.246 A ˚) is shorter than that in the triplet (1.288 A ˚) and resembles a typical C-N double bond (1.25-1.26 A ˚in strained cyclic compounds). [27][28][29] The singlet NCS bond angle (791) is much smaller than that calculated for 3 1 (1111).…”

Section: Structure Of Thiobenzoylnitrenementioning

confidence: 99%

Nanosecond time-resolved IR study of thiobenzoylnitrene

Liu

Evans

Toscano

2012

Phys. Chem. Chem. Phys.

View full text Add to dashboard Cite

Nanosecond time-resolved infrared (TRIR) spectroscopy has been used to observe singlet thiobenzoylnitrene at 1740 cm(-1) upon photolysis of 5-phenyl-1,2,3,4-thiatriazole in acetonitrile and dichloromethane. Consistent with the experimental observations, thiobenzoylnitrene is predicted by B3LYP/6-31G* calculations to have a singlet ground state with an intense IR band at 1752 cm(-1). Phenyl isothiocyanate is also produced. Kinetic measurements indicate that it is not formed from singlet thiobenzoylnitrene, but rather directly from the thiatriazole. Unlike benzoylnitrene, singlet thiobenzoylnitrene does not react with acetonitrile or dichloromethane on the nanosecond timescale. However, it does react with dimethyl sulfoxide (DMSO) to produce a sulfoximine detected at 1180 cm(-1) (k(DMSO) = 3 × 10(5) M(-1) s(-1)). Benzonitrile (observed at 2230 cm(-1)) is produced from both singlet thiobenzoylnitrene (presumably through a short-lived, unobservable benzonitrile sulfide intermediate) and directly from the thiatriazole. B3LYP/6-31G* calculations also show that the structure of singlet thiobenzoylnitrene is analogous to that of related acylnitrenes, with a significant bonding interaction between the nitrogen and sulfur. Triplet thiobenzoylnitrene, on the other hand, is predicted computationally to have a biradical structure.

show abstract

Section: Structure Of Thiobenzoylnitrenementioning

confidence: 99%

Nanosecond time-resolved IR study of thiobenzoylnitrene

Liu

Evans

Toscano

2012

Phys. Chem. Chem. Phys.

View full text Add to dashboard Cite

show abstract

“…The S1ÐC10 [1.740 (2) A Ê ] and S3ÐC11 [1.708 (2) A Ê ] bonds display multiple-bond character. The S1ÐC21 and S3ÐC21 bond lengths are 1.800 (2) and 1.801 (2) A Ê , respectively, and are comparable to the normal CÐS single-bond length [1.79±1.82 (1) A Ê ; Miller et al, 2000].…”

Section: Commentmentioning

confidence: 80%

A metal-mediated dimerization of the ligand bis(N,N-diethylamino)carbeniumdithiocarboxylate

Banerjee

Zubieta

2004

Acta Crystallogr C

View full text Add to dashboard Cite

The title compound, methylene bis[bis(N,N-diethylamino)carbeniumdithiocarboxylate] pentachlorooxorhenium, (C(21)H(42)N(4)S(4))[ReCl(5)O], is the result of an unusual dimerization of the ligand bis(N,N-diethylamino)carbeniumdithiocarboxylate [(Et(2)N)(2)C(2)S(2)] upon reaction with [ReOCl(3)(PPh(3))(2)] in chloroform under reflux conditions. The compound was obtained as a dicationic moiety, with the molecular [ReOCl(5)](2-) anion providing the charge compensation. The planes of the carbenium and thiocarboxylate moieties are nearly perpendicular to one another and the backbone C-C bond length in the N(2)CCS(2) group is the same as a normal C-C single-bond length.

show abstract

“…For general background to bis(N,N-disubstituted amino)carbeniumdithiocarboxylates, see: Winberg & Coffman (1965); Nagasawa et al (1995); Nakayama & Akiyama (1992); Nakayama et al (1997Nakayama et al ( , 2000; Nakayama (2000Nakayama ( , 2002; Miller et al (2000); Fujihara et al (2002); Siemeling et al (2012). For transition metal complexes, see: Miyashita et al (1998); Banerjee et al (2002); Fujihara et al (2004); Sugaya et al (2009).…”

Section: Related Literaturementioning

confidence: 99%

2-{[2,2-Bis(diethylamino)ethan-2-yliumthioyl]sulfanyl}-1,1-bis(diethylamino)ethylium bis(perchlorate)

et al. 2012

View full text Add to dashboard Cite

The title salt, C20H42N4S2 2+·2ClO4 −, was obtained from the reaction of bis(diethylamino)carbeniumdithiocarboxylate, (Et2N)2C2S2, with Fe(ClO4)2·6H2O in CH2Cl2. The title compound, in which one of the S atoms of (Et2N)2C2S2 is bound to a 1,1-bis(diethylamino)ethane moiety, has two carbenium C atoms, and the charge compensation is provided by two perchlorate anions. The N2C—CS2 bond length is 1.512 (4) Å, corresponding to a C—C single bond, and the dihedral angle between N2C– and –CS2 planes [72.0 (2)°] is smaller than that of (Et2N)2C2S2 [82.0 (1)°]. The crystal structure features C—H⋯S hydrogen bonds.

show abstract

Regioselective synthesis, X-ray structure, and reactivity of a tricyclic tetrasulfone, 1,3,5,7-tetramethyl-2,4,6,8,9,10-hexathiatricyclo[3.3.1.13,7]decane 2,2,4,4,6,6,8,8-octaoxide, derived from tetramethylhexathiaadamantane †

Cited by 10 publications

References 10 publications

Nanosecond time-resolved IR study of thiobenzoylnitrene

Nanosecond time-resolved IR study of thiobenzoylnitrene

A metal-mediated dimerization of the ligand bis(N,N-diethylamino)carbeniumdithiocarboxylate

2-{[2,2-Bis(diethylamino)ethan-2-yliumthioyl]sulfanyl}-1,1-bis(diethylamino)ethylium bis(perchlorate)

Contact Info

Product

Resources

About