Organoselenium derivatives of metal carbonyls. Part II. Dimeric and monomeric derivatives of iron carbonyl

Abstract

Dodecacarbonyltri-iron reacts with dimethyl and diethyl diselenides and with the corresponding bisperfluoroalkyl diselenides to afford the respective selenoalkyl and perfluoroalkyl iron tricarbonyl dimers, [Fe(C0),Se(R)I2 (R = CH,, C2H5, CF, , or C2F5), while the i-C3H7 derivative is obtained by the reaction of the same iron carbonyl with perfluoroisopropylselenol. The two compounds of thetype [(C,H,)Fe(CO)Se(R)], (R = C,H,or n-C,H,) resulted from the reaction between the cyclopentadienyl iron dicarbonyl dimer, [(C,H,) Fe(CO),],, and the appropriate dialkyl diselenide.The only monomeric derivatives in this group of compounds, (C,H5)Fe(CO),Se(RF) (RFt = CF, , C2F5, or C3F7), were obtained by the reaction of cyclopentadienyl iron dicarbonyl dimer and the respective bisperfluoroalkyl diselenide.The mechanism of the above reactions is discussed and the properties of the new compounds are described.NUMEROUS derivatives of transition-metal carbonyls or cyclopentadienyl carbonyls also containing organosulphur bridges have been prepared; most of these compounds are either binuclear 2-8 or p o l y n u ~l e a r . ~-~~ However, some derivatives with terminal organosulphur groups are also known.'$ 14-17 Surprisingly, few such t The symbol RF is used throughout this paper to denote a perfluoroalkyl group.

Remarkable Reactions of Cationic Carbyne Complexes of Manganese and Rhenium with Diiron Anions [Fe2(μ-CO)(μ-SeR)(CO)6]-. A Route to RSe-Bridged Dimetal Bridging Carbene Complexes

“…Althuogh several bis(μ-SeR)hexacarbonyldiiron compounds have been synthesized, 11a,,, no X-ray structure of such compounds is known. To firmly confirm their configuration and examine their structural features, a single-crystal X-ray diffraction study was carried out on complex 9 .…”

“…Immediately the brown-red solution turned dark brown. The reaction mixture was slowly warmed to −80 °C and then stirred at −80 to −50 °C for 6−7 h. Further treatment of the resulting mixture as in the reaction of 1 with 3 gave 0.150 g (19%, based on 1 ) of red crystals of 15 and 0.585 g (72%, based on 1 ) of 17 . Product 15 is a red viscous oil at room temperature: IR (CH 2 Cl 2 ) ν(CO) 2061 (s), 2025 (vs), 1985 (vs) cm -1 (lit .…”

“…The reaction mixture was slowly warmed to −80 °C and then stirred at −80 to −50 °C for 6−7 h. Further treatment of the resulting mixture as in the reaction of 1 with 3 gave 0.150 g (19%, based on 1 ) of red crystals of 15 and 0.585 g (72%, based on 1 ) of 17 . Product 15 is a red viscous oil at room temperature: IR (CH 2 Cl 2 ) ν(CO) 2061 (s), 2025 (vs), 1985 (vs) cm -1 (lit . (KBr) 2060 (vs), 2020 (vs), 1985 (vs) cm -1 ); 1 H NMR (CD 3 COCD 3 ) δ 2.75 (m, 4H, CH 3 C H 2 ), 1.48 (m, 6H, C H 3 CH 2 ); MS m / e 498 (M + ), 442 [M + − 2CO], 414 [M + − 3CO], 386 [M + − 4CO], 358 [M + − 5CO], 330 [M + − 6CO].…”