Darstellung und Molekülstruktur von μ‐1,2‐Dithiooxalato ( S,S ′)‐bis[pentacarbonylmangan(I)]

Abstract

Die Struktur der zweikernigen Titelverbindung 2 wurde rontgendiffraktometrisch bestimmt. 2 entsteht durch Reaktion yon Cs,(OSC -CSO) rnit Mn(CO)5Br. Der Thiooxalato-Ligand besitzt transplanare Konformation und verkniipft uber koordinative Mn -S --Bindungen die beiden Molekiilhalften. Preparation and Molecular Structure of p-l,Z-Dithiooralato(S S')-bis[pentacarbonyImanganese( I)]The structure of the binuclear title compound 2 has been determined from X-ray data. 2 is formed by reaction of Cs,(OSC -CSO) with Mn(CO),Br. The thiooxalato ligand has a transplanar conformation and connects the two Mn atoms through dative Mn-S-bonds.

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

“…Compound A shows a similar pattern of n (C^O) absorption bands as its manganese analogue [{Mn(CO) 5 } 2 (m 2 -C 2 S 2 O 2 -k 2 S,S)] [6]. It also shows a sharp IR band at 1645 cm À1 , which is assigned to the noncoordinated C]O groups.…”

“…[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.…”

“…Complex 4, [Re 2 (m-dppene)(CO) 6 (cis-m,h 2 :h 2 -C 2 O 2 N 2 H 2 )] was obtained in low yield together with the bis-dppene-bridged compound [Re 2 (m-dppene) 2 (CF 3 SO 3 ) 2 (CO) 6 ] 5 (Scheme 4). The low yield of 4 and the formation of a significant amount of the oxamide-free compound, 5, are probably due to the low solubility of oxamide in THF (solvent for the reaction).…”

“…The solvent was removed under reduced pressure, and the residue was dissolved in a minimum amount of CH 2 Cl 2 . Layering with hexane gave a dark red precipitate, which was washed with hexane and dried under high vacuum to give [Re 2 (CO) 6 were filtered off by suction, and [NEt 4 ] 2 [C 2 S 4 ] (0.011 g, 0.027 mmol) was added to the filtrate. The dark blue mixture formed was stirred at r.t. for 26 h before being filtered again.…”

“…The bis(bidentate) ligands generally form the shorter edges of the rectangle, while rigid exo-bidentate ligands, such as 4,4 0 -bipyridine and trans-1,2-bis(pyridyl)ethylene [1], are used to form the longer edges. Linear oligomers/polymers or catenanes can, in principle, also be formed in the reaction of exo-bidentate ligands with {Re 2 (CO) 6 L} units [L ¼ bis(bidentate) ligand]. We have studied the reaction of [Re 2 (CO) 6 (m,h 2 :h 2 -C 2 O 4 )] n with trans-1,2-bis(diphenylphosphino)-ethylene (dppene).…”