Nitroxide chemistry. Part X. Reactions of NN-bistrifluoromethyl-amino-oxyl with alkyltrihalogenosilanes and vinylsilanes; rearrangement of (1 -NN-bistrifluoromethylamino-oxyalkyl)silanes
作者:Robert N. Haszeldine、David J. Rogers、Anthony E. Tipping
DOI:10.1039/dt9760001056
日期:——
The reactions of the oxyl (CF3)2N·O˙ with various alkyltrichlorosilanes and alkyltrifluorosilanes show that the α position of the alkyl group is deactivated towards radical attack and the effect is more pronounced with alkyltrichlorosilanes. A novel rearrangement of type N·O·C·Si→N·C·O·Si occurs on heating (1-NN-bistrifluoromethyl-amino-oxyalkyl)silanes, and the ease of rearrangement is in the order
Synthesis, Structure, and Spectroscopy of Silaallyl− and Silapentadienyl−Iridium−Phosphine Complexes<sup>1</sup>
作者:John R. Bleeke、Todsapon Thananatthanachon、Nigam P. Rath
DOI:10.1021/om700487n
日期:2007.7.30
Silaallyl− and silapentadienyl−iridium−phosphinecomplexes have been synthesized via the reaction of “(Me)Ir(PMe3)3” with vinyl- and butadienyldimethylsilanes. Upon heating, these complexes lose methane and undergo a variety of reactions, including C−H bond activation to produce a five-membered iridasilacycle, CC bond coordination to generate an η1,η2-silapentadienyl ligand, and decomposition.
Photochemical studies of (η<sup>5</sup>-C<sub>5</sub>H<sub>5</sub>)Ru(PPh<sub>3</sub>)<sub>2</sub>Cl and (η<sup>5</sup>-C<sub>5</sub>H<sub>5</sub>)Ru(PPh<sub>3</sub>)<sub>2</sub>Me: formation of Si–H and C–H bond activation products
作者:Johnathan L. Clark、Simon B. Duckett
DOI:10.1039/c3dt52069b
日期:——
CpRu(PEt3)2Cl can be formed. Room temperature irradiation of the related complex CpRu(PPh3)2Me with L = PEt3, C2H4, and DMSO also produces CpRu(PPh3)(L)Me. However, when these reactions are followed by in situ laser irradiation (325 nm source) at low temperature, three solvent activated isomers (ortho, meta and para) of CpRu(PPh3)2(C6H4Me) are detected in toluene in addition to η1- and η3-coordinated
研究CpRu(PPh 3)2 Cl和CpRu(PPh 3)2 Me对两个电子给体配体PEt 3,C 2 H 4,DMSO,CH键可活化试剂四氢呋喃,甲苯和吡啶的光化学反应性的研究,以及给出了SiH键可活化试剂HSiEt 3和HSi(Me)2 CH CH 2)。CpRu(PPh 3)2 Cl的宽带紫外线照射导致单取代产物的形成,例如CpRu(PPh 3)(PEt 3尽管可以形成热双取代的产物,如CpRu(PEt 3)2 Cl ,但对进一步的光化学反应呈惰性。在室温下辐照L = PEt 3,C 2 H 4和DMSO的相关复合物CpRu(PPh 3)2 Me也会产生CpRu(PPh 3)(L)Me。但是,在低温下进行原位激光照射(325 nm源)进行这些反应后,CpRu(PPh 3)2(C 6 H )的三种溶剂活化的异构体(邻位,间位和对位)4 Me)中的甲苯中检测除了η 1 -和η 3个配位的
Cobalt-Catalyzed Hydrosilation/Hydrogen-Transfer Cascade Reaction: A New Route to Silyl Enol Ethers
作者:Thomas W. Lyons、Maurice Brookhart
DOI:10.1002/chem.201301502
日期:2013.7.29
Capitalizing on cobalt: A new route to silyl enol ethers employing a Co‐catalyzed cascade reaction featuring a tandem hydrosilation/hydrogen‐transfer reaction is reported. The low catalyst loading, mild reaction conditions, and unique η2‐silane resting state showcase the impressive utility of this seldom used transition‐metal catalyst in CH activation reactions (see scheme; VTMS = vinyltrimethylsilane;