Darstellung und Charakterisierung des Zwitterions S₂C—C(NMe₂)₂; eine übergangsmetallinduzierte C—C-Kopplung. Komplexchemie der Zwitterionen S₂C—C(NR₂)₂ / Synthesis and Characterization of the Zwitter Ion S₂C —C(NMe₂)₂; a Transition Metal Induced C —C Coupling. Complex Chemistry of the Zwitter Ions S₂C —C(NR₂)₂

Abstract

<jats:p>A transition metal induced C-C coupling by the reaction of W<jats:sub>2</jats:sub>(N(CH<jats:sub>3</jats:sub>)<jats:sub>2</jats:sub>)<jats:sub>6</jats:sub>, (4) and CS<jats:sub>2</jats:sub> yielded the zwitter ion S<jats:sub>2</jats:sub>C-C(N(CH<jats:sub>3</jats:sub>)<jats:sub>2</jats:sub>)<jats:sub>2</jats:sub> (1d) besides W<jats:sub>2</jats:sub>(N(CH<jats:sub>3</jats:sub>)<jats:sub>2</jats:sub>)<jats:sub>2</jats:sub>(CS<jats:sub>2</jats:sub>)<jats:sub>2</jats:sub>S<jats:sub>4</jats:sub> (5). The com- plex chemistry of the zwitter ions 1d and S<jats:sub>2</jats:sub>CC(N(CH<jats:sub>2</jats:sub>)<jats:sub>4</jats:sub>X)<jats:sub>2</jats:sub> (X = CH<jats:sub>2</jats:sub>, O) has been investigated by their reaction with (η<jats:sup>5</jats:sup>-C<jats:sub>5</jats:sub>H<jats:sub>5</jats:sub>)<jats:sub>2</jats:sub>Mo<jats:sub>2</jats:sub>(CO)<jats:sub>4</jats:sub> (2) and (η<jats:sup>5</jats:sup>-C<jats:sub>5</jats:sub>H<jats:sub>5</jats:sub>)Mo(CO)<jats:sub>3</jats:sub>Cl (3). Reaction of the former led to complexes (η<jats:sup>5</jats:sup>-C<jats:sub>5</jats:sub>H<jats:sub>5</jats:sub>)Mo(CO)<jats:sub>2</jats:sub>(S<jats:sub>2</jats:sub>CR) (R = N(CH<jats:sub>3</jats:sub>)<jats:sub>2</jats:sub>, N(CH<jats:sub>2</jats:sub>)<jats:sub>4</jats:sub>X) and the new compounds [(η<jats:sup>5</jats:sup>-C<jats:sub>5</jats:sub>H<jats:sub>5</jats:sub>)Mo(CO)<jats:sub>2</jats:sub>(S<jats:sub>2</jats:sub>C-CR<jats:sub>2</jats:sub>)]<jats:sup>+</jats:sup>. X-ray structure analyses of 1d and ((η<jats:sup>5</jats:sup>-C<jats:sub>5</jats:sub>H<jats:sub>5</jats:sub>)Mo(CO)<jats:sub>2</jats:sub>(S<jats:sub>2</jats:sub>C-C(N(CH<jats:sub>2</jats:sub>)<jats:sub>5</jats:sub>)<jats:sub>2</jats:sub>)]<jats:sup>⊕</jats:sup>PF<jats:sub>6</jats:sub><jats:sup>⊖ </jats:sup>(10b) are described. </jats:p>

The stable inner salt 2,2-dimorpholino-2-ethylium-1-dithioate

“…Their thermodynamic stability apparently comes from localization of the positive and negative charges on the NÐCÐN and SÐCÐS moieties, respectively. The most remarkable structural characteristic of these compounds is that the planes of the CS 2 and CN 2 groups are almost perpendicular (Sheldrick et al, 1980;Ziegler et al, 1987;Borer et al, 1989;Kuhn et al, 1987;Nagasawa et al, 1995;Nakayama et al, 2000). We report here the characteristic molecular conformation of the title compound, (I), in the solid state ( Fig.…”

Zur Reaktion von Carben-Addukten des Kohlenstoffdisulfids mit Brom und Iod [1] / On the Reaction of Carbene Adducts of Carbon Disulfide with Bromine and Iodine [1]

“…Im IR-Spektrum ist die für die Substanzklasse charak teristische intensive Schwingung vCS2 im Bereich von ca. 1050 cm -1 sichtbar [5][6][7], die analog auch für die A ddukte des Typs R3 P C S 2 beobachtet wird [8 ]. In den M assenspektren tritt der Molekül- …”

“…Durch ihre erfolgreiche Isolierung [2,3] stehen Imidazol-2-ylidene (1) als R eaktionsspartner für anorganische Elektrophile zur Verfügung [4], Addukte nucleophiler Carbene mit CS2 sind bislang nur vereinzelt bekannt geworden (2; (R 2 N)2C = 1,3-Diethylimidazolidin [5], Dipiperidinylmethylen, Dim orpholinylm ethylen [6 ], Bis(dimethylamino)m ethylen [7]). Die leichte Verfügbarkeit von 1 legte nun die Synthese der A ddukte 3 nahe.…”

Tetrakis(1,3-dimethylimidazolidinium-2-dithiocarboxylate-κS)zinc(II) diperchlorate

“…Their thermodynamic stability is apparently due to delocalization of the positive and the negative charges on the NÐCÐN and the SÐCÐS moieties, respectively. The most remarkable structural characteristic of these compounds is that the CS 2 and CN 2 groups are almost perpendicular (Sheldrick et al, 1980;Ziegler et al, 1987;Borer et al, 1989;Kuhn et al, 1987;Nagasawa et al, 1995;Nakayama et al, 2000;Fujihara et al, 2002). We report here the structure of the title complex, (I) (Fig.…”