944147-17-5Relevant academic research and scientific papers
Preparation of (n5-C5Me5)2Th(bipy) and Its Reactivity toward Small Molecules
Yang, Pikun,Zhou, Enwei,Fang, Bo,Hou, Guohua,Zi, Guofu,Walter, Marc D.
, p. 2129 - 2139 (2016)
Reduction of (n5-C5Me5)2ThCl2 (1) with potassium graphite (KC8) in the presence of 2,2′-bipyridine forms the thorium bipy metallocene (n5-C5Me5)2Th(bipy) (2) in good yield. Complex 2 was fully characterized and reacts with various small molecules. For example, 2 serves as a source for the (n5-C5Me5)2Th(II) fragment when exposed to conjugated alkynes, elemental sulfur and their organic derivatives, diazabutadiene, carbodiimide, CS2, isothiocyanate, and organic azides. Furthermore, treatment of 2 with ketone Ph2CO, thio-ketone Ph2CS, imine PhCH=NPh, and nitrile PhCN results in C-C bond coupling products (n5-C5Me5)2Th[(bipy)(Ph2CO)] (10), (n5-C5Me5)2Th[(bipy)(Ph2CS)] (11), (n5-C5Me5)2Th[(bipy)(PhCHNPh)] (12), and (n5-C5Me5)2Th[(bipy)(PhCN)] (13), respectively, in quantitative conversion.
Phenylsilane as a safe, versatile alternative to hydrogen for the synthesis of actinide hydrides
Pagano, Justin K.,Dorhout, Jacquelyn M.,Waterman, Rory,Czerwinski, Kenneth R.,Kiplinger, Jaqueline L.
supporting information, p. 17379 - 17381 (2015/12/09)
The thorium and uranium dihydride dimer complexes [(C5Me5)2An(H)(μ-H)]2 (An = Th, U) have been easily prepared using phenylsilane, which is an efficient and safer alternative to hydrogen gas. The synthetic utili
Actinide hydride complexes as multielectron reductants: Analogous reduction chemistry from [(C5Me5)2UH]2, [(C5Me5)2UH2]2, and [(C5Me5)2ThH2]2
Evans, William J.,Miller, Kevin A.,Kozimor, Stosh A.,Ziller, Joseph W.,DiPasquale, Antonio G.,Rheingold, Arnold L.
, p. 3568 - 3576 (2008/10/09)
Methods to separate the components of the equilibrium mixture of [(C 5Me5)2UH]2 and [(C 5Me5)2-UH]2 have been developed that allow their reductive chemistry to be studied. These actinide hydrides can act as four-, six-, and eight-electron reductants depending on the substrate with H: as the byproduct of a H- → e- + 1/2 H2 redox couple. This hydride reduction chemistry allows complexes of redox-inactive Th4+ such as [(C5Me5) 2THH2]2 to be four- and six-electron reductants. [(C5Me5)2UH]2 and [(C5-Me5)2UH2]2 cleanly reduce 2 equiv of PhEEPh (E = S, Se) to form 2 equiv of (C5Me 5)2U(SPh)2 and (C5Me 5)2U(SePh)2 in an overall four-electron reduction in each case. [(C5Me5)2UH] 2 and [(C5Me5)2UH2] 2 also effect a six-electron reduction of 3 equiv of 1,3,5,7-cyclooctatetraene to [(C5Me5)(C8H 8)]2-(C8H8) and an eight-electron reduction of 2 equiv of PhN=NPh to form 2 equiv of the U6+ imido complex (C5Me5)2U(=NPh)2. In each reaction, H2 is a byproduct. This hydride-based reduction is also successful with the tetravalent thorium hydride [(C5Me 5)2THH2]2 which reduces 2 equiv of PhSSPh to (C5Me5)2-Th(SPh)2 and 3 equiv of C8H8 to [(C5Me5)(C 8H8)Th]2(C8H8) with concomitant formation of H2. X-ray crystallographic data are reported on [(C5Me5)2UH]2, [(C 5Me5)2UH2]2, and (C 5Me5)2U(SePh)2 as well as the thorium reduction products (C5Me5)2Th(SPh) 2 and [(C5Me5)(C8H 8)Th]2(C8H8).
