Double Silyl Migration Converting ORe[N(SiMe2CH2PCy2)2] to NRe[O(SiMe2CH2PCy2)2] Substructures

Autor:	Oleg V. Ozerov, John C. Huffman, Hélène Gérard, Kenneth G. Caulton, Lori A. Watson
Rok vydání:	2002
Předmět:	Inorganic Chemistry Silylation Chemistry Stereochemistry Thermal decomposition Structural isomer Halide Chemical stability Physical and Theoretical Chemistry Medicinal chemistry
Zdroj:	Inorganic Chemistry. 41:5615-5625
ISSN:	1520-510X 0020-1669
Popis:	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.
Databáze:	OpenAIRE
Externí odkaz:	https://explore.openaire.eu/search/publication?articleId=doi_dedup___::8dcd1f6bc4189c4b092b7a75f6a5afd9 https://doi.org/10.1021/ic020424p Zobrazit plný text záznamu