1227297-30-4Relevant articles and documents
Highly selective conversion of nitrobenzenes using a simple reducing system combined with a trivalent indium salt and a hydrosilane
Sakai, Norio,Fujii, Kohji,Nabeshima, Shinya,Ikeda, Reiko,Konakahara, Takeo
, p. 3173 - 3175 (2010)
Controlling the type of indium salt and hydrosilane enables a highly selective reduction of aromatic nitro compounds into three coupling compounds, azoxybenzenes, azobenzenes and diphenylhydrazines, and one reductive compound, anilines. The Royal Society of Chemistry 2010.
When Do Strongly Coupled Diradicals Show Strongly Coupled Reactivity? Thermodynamics and Kinetics of Hydrogen Atom Transfer Reactions of Palladium and Platinum Bis(iminosemiquinone) Complexes
Conner, Kyle M.,Arostegui, AnnaMaria C.,Swanson, Daniel D.,Brown, Seth N.
, p. 9696 - 9707 (2018/08/28)
The 2,2′-biphenylene-bridged bis(iminosemiquinone) complexes (tBuClip)M [tBuClipH4 = 4,4′-di-tert-butyl-N,N′-bis(3,5-di-tert-butyl-2-hydroxyphenyl)-2,2′-diaminobiphenyl; M = Pd, Pt] can be reduced to the bis(aminophenoxide) complexes (tBuClipH2)M by reaction with hydrazobenzene (M = Pd) or by catalytic hydrogenation (M = Pt). The palladium complex with one aminophenoxide ligand and one iminosemiquinone ligand, (tBuClipH)Pd, is generated by comproportionation of (tBuClip)Pd with (tBuClipH2)Pd in a process that is both slow (0.06 M-1 s-1 in toluene at 23 °C) and only modestly favorable (Kcom = 1.9 in CDCl3), indicating that both N-H bonds have essentially the same bond strength. The mono(iminoquinone) complex (tBuClipH)Pt has not been observed, indicating that the platinum analogue shows no tendency to comproportionate (Kcom tBuClipH2)Pt to (tBuClip)Pd occurring with ?G° = ?8.9 kcal mol-1. The palladium complex (tBuClipH2)Pd reacts with nitroxyl radicals in two observable steps, with the first hydrogen transfer taking place slightly faster than the second. In the platinum analogue, the first hydrogen transfer is much slower than the second, presumably because the N-H bond in the monoradical complex (tBuClipH)Pt is unusually weak. Using driving force-rate correlations, it is estimated that this bond has a BDFE of 55.1 kcal mol-1, which is 7.1 kcal mol-1 weaker than that of the first N-H bond in (tBuClipH2)Pt. The two radical centers in the platinum, but not the palladium, complex thus act in concert with each other and display a strong thermodynamic bias toward two-electron reactivity. The greater thermodynamic and kinetic coupling in the platinum complex is attributed to the stronger metal-ligand ? interactions in this compound.
