Iron‐Catalyzed Dehydrogenative Coupling of Tertiary Silanes

(Me3N)Mo(CO)5-Catalyzed Reduction of DMF by Disiloxane and Disilane Moieties: Fate of the Silicon-Containing Fragments

“…Although the chemistry was first noted in 1985 for the reduction of DMF along with the formation of disiloxanes, only recently has it developed into a reaction of choice due to its mildness and selectivity in comparison to classical methods . We recently reported the reduction of simple formamides to amines using silanes, germanes, and stannanes with concomitant formation of disiloxanes, digermoxanes, and distannoxanes using Mo(CO) 6 , (Me 3 N)Mo(CO) 5 , (η 5 -C 5 H 5 )Fe(CO) 2 CH 3 (FpMe), (η 5 -C 5 H 5 )Mo(CO) 3 CH 3 (MpMe), and (η 5 -C 5 H 5 )Mn(CO) 3 as catalysts . For the reactions using Mo(CO) 6 and (Me 3 N)Mo(CO) 5 we proposed a stepwise reduction mechanism based upon our first-time observation and isolation of the initial hydrosilylation products, i.e.…”

Desulfurization of N,N-dimethylthioformamide by hydrosilane with the help of an iron complex. Isolation and characterization of an iron–carbene complex as an intermediate of CS double bond cleavage

“…5 Iron is one of the best candidates as precious metal surrogates because of its price, abundance, and environmental compatibility. 6 Pannell's group 7 and our group 8 recently reported that Cp(CO) 2 FeMe (Cp = Z 5 -C 5 H 5 ) (1) serves as a good catalyst for deoxygenation of dimethylformamide (DMF) with Et 3 SiH. Although some catalytic reaction mechanisms have been proposed, there is no convincing mechanism.…”

Polyferrocenyldisiloxane from the Platinum-Catalyzed Reactions of Tertiary Bis(dimethylsilyl)ferrocene in a Polar Aprotic Solvent

“…Our current efforts, 12 a reinterpretation of the original report, 13 and others 14 have now correctly identified the polyferrocenyldisiloxane 8 as the main product of those reactions, along with detectable quantities of NMe 3 and H 2 (g). 11 It is of interest to note that ambient Fe-catalyzed (1:25 [cat.…”

“…21,22 A further separation of the higher molecular weight oligomeric materials from the Ptcatalyzed equimolar reactions of 6 and 14 (DMF) by preparative TLC afforded the trimer 9b and tetramer 9c (Figure 3) in decreasing relative yields. Oligomers 9b and 9c were readily characterized by 1 H, 13 C, and 29 Si NMR spectroscopy and further confirmed via HR-MS. Our investigation found that the reaction 6 with Karstedt's catalyst in DMF solutions at elevated temperatures yielded a linear polyferrocenyldisiloxane 8 and shorter chain linear and cyclic oligoferrocenylsiloxanes 9a-c, 10, and 11a-c. Polymerization Note is consistent with a concomitant oxidation of the ferrocenylsilane and the stoichometric reduction of the solvent. The Pt-catalyzed coupling reactions of 6 in DMSO solutions proceed much more quickly than in DMF solutions under ambient or elevated temperatures.…”