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

Abstract

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.

trans-{1,8-Bis[(S)-1-phenylethyl]-1,3,6,8,10,13-hexaazacyclotetradecane}bis(thiocyanato-κN)copper(II)

“…In the coordinated thiocyanate ions, the average N-C and C-S bond distances are 1.160 (6) and 1.638 (5) Å, respectively. The former is very similar to CN triple bond length, while the latter is slightly shorter than the normal CS single bond distance (Stølevik & Postmyr, 1997;Banerjee & Zubieta, 2004). The pendant arms of azamacrocyclic ligand have chiral carbon atoms (S type).…”

trans-{1,8-Bis[(R)-α-methylbenzyl]-1,3,6,8,10,13-hexaazacyclotetradecane}dithiocyanatonickel(II)

“…The former is very similar to a CN triple bond length, while the latter is slightly shorter than the normal CS single bond distance (Stølevik & Postmyr, 1997;Banerjee & Zubieta, 2004 (Table 1), which give rise to one-dimensional polymeric chains propagating along the a axis ( Figure 2). The shortest Ni•••Ni intrachain separation within the hydrogen-bonded one-dimensional polymer is 8.531 (1) Å and is about 5% longer than the shortest interchain Ni…”

“…For general background, see: Banerjee & Zubieta (2004); Du et al (2003); Gao et al (2005); Han et al (2008); Katsuki et al (2000); Lehn (1995); Leonard et al (2007); Stølevik & Postmyr (1997).…”

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

“…For transition metal complexes, see: Miyashita et al (1998); Banerjee et al (2002); Fujihara et al (2004); Sugaya et al (2009). For the cationic dimer of bis(N,N-disubstituted amino)carbeniumdithiocarboxylates, see: Otani et al (1998); Banerjee & Zubieta (2004). For reference bond-length data, see: Allen et al (1987).…”

“…, which have a zwitterionic (inner-salt) form and a neutral form as canonical structures (Nagasawa et al, 1995;Fujihara et al, 2002), are structurally and reactively interesting (Winberg & Coffman, 1965;Otani et al, 1998;Nakayama & Akiyama, 1992;Nakayama et al, 2000;Nakayama, 2000Nakayama, , 2002Banerjee & Zubieta, 2004;Siemeling et al, 2012). We have reported the syntheses, structures, and properties of the various transition metal complexes using (R 2 N) 2 C 2 S 2 as ligands (Miyashita et al, 1998;Banerjee et al, 2002;Fujihara et al, 2004;Sugaya et al, 2009), and the ligands act as neutral monodentate, bridging, and chelating ligands maintaining the characteristic zwitterionic form.…”