C−S Bond Activation of Two Novel Asymmetric α-azo-Ketenedithioacetals Using Fe₂(CO)₉

Abstract

Two novel asymmetric azo-aliphatic compounds [(CH3)3CNNC(S(CH2) n S)C(O)CH3, n = 2 (5) and n = 3 (6)] have been synthesized via a tandem procedure. The reaction of 5 and 6 with Fe2(CO)9 affords three novel dinuclear iron complexes displaying C−S bond activation (5b, 5c, and 6c). 5b and 5c exhibit an unusual stereochemistry about the Fe2 unit, as revealed by X-ray diffraction analyses. Additionally, two alquildithiolate-bridged iron hexacarbonyl complexes (5a and 6a) were obtained as a result of a double C−S bond activation from 5 and 6, respectively. The structures of 5, 5b, and 5c were fully established by X-ray diffraction analyses.

Synthesis of Diiron(I) Dithiolato Carbonyl Complexes

“…221 Rings with several heteroatoms, e.g., the groups –S–CH 2 –S–C and C–S–CH 2 –CH 2 –S–, appear especially susceptible to activation by Fe(0). 222–224 The methane- and ethanedithiolate Fe 2 ( μ -S 2 (CH 2 ) 2 )(CO) 6 arise (no yields being mentioned) from the reaction of Fe 3 (CO) 12 with 1,4-dithiane and 1,3,5-trithiane (SCH 2 ) 3 , respectively. 225 The thiol route (CH 2 (SH) 2 + Fe 3 (CO) 12 ) is far more efficient (Scheme 18).…”

Mass spectrometric and theoretical studies on dissociation of the CS bond in the benzenesulfonic acid and benzenesulfinic acid anion series: Homolytic cleavage vs heterolytic cleavage

“…Activation and cleavage of the CAS bond is a critical component in the study of the organosulfur chemistry [1][2][3][4][5][6][7][8][9][10][11][12][13][14][15][16][17]. A case for example is the hydrodesulfurization (HDS) process in the chemical industry.…”

Recent developments of ketene dithioacetal chemistry

“…Several complexes based on ketene dithioacetals have been studied, [288][289][290] and have been shown to display C-S bond activation and subtle ring size effects on bonding mode. This is exemplified in the cases of the structures and properties of (diamine)platinum(II) complexes involving sulfur-containing dicarboxylate ligands containing a 1,3-dithiolane, 1,3-dithlane, and 1,3-dithiepane moieties, respectively (Fig.…”