title: Double silyl migration converting ORe[N(SiMe(2)CH(2)PCy(2))(2)] to NRe[O(SiMe(2)CH(2)PCy(2))(2)] substructures.
abstract: The reaction of (R(2)PCH(2)SiMe(2))(2)NM (PNP(R)M; R = Cy; M = Li, Na, MgHal, Ag) with L(2)ReOX(3) [L(2) = (Ph(3)P)(2) or (Ph(3)PO)(Me(2)S); X = Cl, Br] gives (PNP(Cy))ReOX(2) as two isomers, mer,trans and mer,cis. These compounds undergo a double Si migration from N to O at 90 degrees C to form (POP(Cy))ReNX(2) as a mixture of mer,trans and fac,cis isomers. Additional thermolysis effects migration of CH(3) from Si to Re, along with compensating migration of halide from Re to Si. DFT calculations on various structural isomers support the greater thermodynamic stability of the POP/ReN isomer vs PNP/ReO and highlight the influence of the template effect on the reactivities of these species.
authors.affiliation: Department of Chemistry and Molecular Structure Center, Indiana University, Bloomington, IN 47405, USA.
authors.forename: Oleg V
authors.initials: OV
authors.lastname: Ozerov
authors.forename: Hélène F
authors.initials: HF
authors.lastname: Gerard
authors.forename: Lori A
authors.initials: LA
authors.lastname: Watson
authors.forename: John C
authors.initials: JC
authors.lastname: Huffman
authors.forename: Kenneth G
authors.initials: KG
authors.lastname: Caulton