RESUMO
The silylation of a phosphine of OsH6 (Pi Pr3 )2 is performed via net-metathesis between Si-C(spn ) and H-C(sp3 ) σ-bonds (n=2, 3). Complex OsH6 (Pi Pr3 )2 activates the Si-H bond of Et3 SiH and Ph3 SiH to give OsH5 (SiR3 )(Pi Pr3 )2 , which yield OsH4 {κ1 -P,η2 -SiH-[i Pr2 PCH(Me)CH2 SiR2 H]}(Pi Pr3 ) and R-H (R=Et, Ph), by displacement of a silyl substituent with a methyl group of a phosphine. Such displacement is a first-order process, with activation entropy consistent with a rate determining step occurring via a highly ordered transition state. It displays selectivity, releasing the hydrocarbon resulting from the rupture of the weakest Si-substituent bond, when the silyl ligand bears different substituents. Accordingly, reactions of OsH6 (Pi Pr3 )2 with dimethylphenylsilane, and 1,1,1,3,5,5,5-heptamethyltrisiloxane afford OsH5 (SiR2 R')(Pi Pr3 )2 , which evolve into OsH4 {κ1 -P,η2 -GeH-[i Pr2 PCH(Me)CH2 SiR2 H]}(Pi Pr3 ) (R=Me, OSiMe3 ) and R'-H (R'=Ph, Me). Exchange reaction is extended to Et3 GeH. The latter reacts with OsH6 (Pi Pr3 )2 to give OsH5 (GeEt3 )(Pi Pr3 )2 , which loses ethane to form OsH4 {κ1 -P,η2 -GeH-[i Pr2 PCH(Me)CH2 GeEt2 H]}(Pi Pr3 ).
RESUMO
Superconductivity (SC) was experimentally observed for the first time in antimony polyhydride. The diamond anvil cell combined with a laser heating system was used to synthesize the antimony polyhydride sample at high pressure and high temperature. In-situ high pressure transport measurements as a function of temperature with an applied magnetic field were performed to study the SC properties. It was found that the antimony polyhydride samples show superconducting transition with critical temperature T c 116 K at 184 GPa. The investigation of SC at magnetic field revealed the superconducting coherent length of â¼40 Å based on the Ginzburg Landau (GL) equation. Antimony polyhydride superconductor has the second highest T c in addition to sulfur hydride among the polyhydrides of elements from main groups IIIA to VIIA in the periodic table.