Reactions of Selected Aromatic Thioketones with Dodecarbonyltriiron

Abstract

Dodecacarbonyltriiron reacts with 3,3,5,5‐tetraphenyl‐1,2,4‐trithiolanes (1e) to give the ortho‐metalated complex Fe2(CO)6[κ,μ‐S,η2‐(C13H10S)] (9a), complexes of the type (Ph2C)S2Fe2(CO)6 and the well known trinuclear complex Fe3S2 (CO)9 as by‐products. Complex 9a can also be obtained from the reaction of Fe3(CO)12 with thiobenzophenone (2a). In a similar way, 4,4′‐bis(dimethylamino)thiobenzophenone (2b) reacts with Fe3(CO)12 to give Fe2(CO)6[κ,μ‐S,η2‐(C17H20N2S)] (9b). The cyclic aromatic thioketones such as dibenzosuberenethione (2c) and xanthione (2d) react with Fe3(CO)12 to give the cyclometalated products Fe2(CO)6[κ,μ‐S,η2‐(C15H12S)] (9c) and Fe2(CO)6[κ,μ‐S,η2‐(C13H8OS)] (9d), respectively, and a small amount of Fe3S2(CO)9. Complexes 9a–d have been characterized by IR and NMR spectroscopies, elemental analyses, and X‐ray single crystal structure analyses.

Synthesis of Diiron(I) Dithiolato Carbonyl Complexes

“…243,245,255,256 C–H activation occurs in these, as illustrated by one of the products in Scheme 22. 243 …”

“…253,254 This trithiolane exists in equilibrium, rapid near 50 °C, with Ph 2 CS and, possibly, the thione-sulfide/dithiirane isomers of Ph 2 CS 2 (Scheme 21). 245 …”

Rational Synthesis of the Carbonyl(perthiolato)diiron [Fe2(S3CPh2)(CO)6] and Related Complexes

“…[10] The diphenylmethanedithiolate has been obtained in 5–25 % yield by the reaction of thiobenzophenone with Fe 2 (CO) 9 and Fe 3 (CO) 12 . [11] These reactions also produce several other products, including Fe 3 S 2 (CO) 9 . From the perspective of stoichiometry, this triiron cluster is a logical precursor to Fe 2 (S 2 CPh 2 )(CO) 6 .…”

“…Indeed, the intermediacy of the dithiirane Ph 2 CS 2 has been proposed for related reactions. [11b,11c,12] …”

Electrochemical Proton Reduction Catalyzed by [Fe2(CO)6{μ‐(TeCH2Te)}] Model that Mimics the Structure of the Active Site of [FeFe]‐Hydrogenase

“…[2][3][4][5] Several model complexes mimicking the active site of the [FeFe]-hydrogenase have been synthesized, characterized, and their catalytic applications have been studied in detail. [6][7][8][9][10][11][12][13] In two recent papers we described the influence of the presence of the Sn atom in μ-(XCH 2 ) 2 SnMe 2 (X = S or Se) linker of the synthetic H-cluster mimics (Figure 1). [14,15] and 125 Te{ 1 H} NMR) as well as X-ray diffraction analysis.…”