1,2‐Dithiooxalatokomplexe von Rhenium(I) und Rhenium(V)

Abstract

Der bei der Umsetzung von Cäsium‐1,2‐dithiooxalat (Cs2dtox) mit Re(CO)5Br entstehende zweikernige Komplex Cs4[Re2(CO)6(dtox)3] enthält ein dtox‐Ion als transplanaren Brückenliganden und zwei chelatartig gebundene Liganden. Die Struktur des durch Reaktion von Cs2[ReOCl5] mit Cs2dtox erhaltenen Cs[ReO(dtox)2] wurde röntgendiffraktometrisch bestimmt. Re ist quadratisch pyramidal von 4 Schwefelatomen und dem Sauerstoffatom koordiniert. Das Re‐Atom liegt 0,752 Å über der Basisfläche, die von den 4 Schwefelatomen gebildet wird. Die IR‐Spektren beider Verbindungen werden zugeordnet.

Formation of “A-frame” dirhenium(I) hexacarbonyl complexes by trans-1,2-bis(diphenylphosphino)ethylene and bis(bidentate) ligands

“…[Re 2 (m-dppene)(CO) 6 5 } 2 (m 2 -C 2 S 4 -k 2 S,S)]. The displacement of an additional CO group on each rhenium atom by tetrathiooxalate is probably favoured due to the greater stability of ReeS bonds.…”

“…The latter is analogous to [Re 2 (CO) 6 (m,h 2 :h 2 -C 2 O 4 )] n , which is formed by the thermal decarbonylation (1 h in refluxing THF) of [{Re(CO) 5 …”

“…Solvents were dried by standard methods [20] and distilled under nitrogen prior to use. The compounds [Re(CO) 5 [24] were prepared by published procedures. Preparative TLC was carried out on pre-coated silica plates of layer thickness 0.25 mm.…”

“…This structure, with almost perfectly eclipsed ReeP bonds (ReeP/PeRe torsional angle of 0.7 ) and a rather short Re/Re distance (5. The facile formation of [Re 2 (m-dppene)(CO) 6 (m,h 2 :h 2 -C 2 O 4 )] and its stability raised the possibility of preparing analogous complexes, wherein the oxalate ligand is replaced by 1,2-dithioooxalate (dto), tetrathiooxalate (tto), dithiooxamidate (dtox) or oxamidate (oxa) (Scheme 1). To our knowledge, no rhenium(I) carbonyl complexes, except Cs 4 [Re 2 (CO) 6 (dto) 3 ] [5], have been reported for the latter ligands. In this paper, we report the synthesis and spectroscopic characterisation of the complexes [Re 2 (m-dppene)(CO) 6 (m,h 2 :h 2 -L)] (L ¼ dto, 1; tto, 2; dtox, 3; oxa, 4).…”

Transition metal complexes containing the 1,2-dicarba-closo-dodecaborane-1,2-dithiolate ligand: crystal structures of [4-MeC5H4NMe]2[Pd(S2C2B10H10)I2], [NEt3H][Mo(η5-C5H5)(NO)(S2C2B10H10)I], [NBu4][Re(O)(S2C2B10H10)2] and [4-MeC5H4NMe]2[{Mo(O)(μ-O)(S2C2B10H10)}2]

“…The C᎐S bonds are only slightly shorter than the standard single bond value, indicating an only relatively small degree of π-electron delocalisation between the sulfur and the carborane cage (see Table 1). For comparison, C᎐S bond lengths in M(SC᎐ ᎐ CS) (M = Pd, Mo or Re) moieties, which might be expected to show some electron delocalisation, average 16 17 and the bis(ethane-1,2-dithiolato)oxorhenium() 18 anions. In the former, which allows conjugation in the S᎐C᎐ ᎐ O system, C᎐S bonds are in the range 1.730-1.766 Å, mean 1.742(8) Å, whereas in the latter, saturated system, C᎐S bonds are 1.795-1.849, mean 1.809 Å.…”