Square-planar bis(triisopropylstibine)(olefin)iridium(I) complexes and their rearrangement to (eta(3)-allyl)hydridoiridium(III) isomers

Citation
Da. Ortmann et al., Square-planar bis(triisopropylstibine)(olefin)iridium(I) complexes and their rearrangement to (eta(3)-allyl)hydridoiridium(III) isomers, ORGANOMETAL, 20(9), 2001, pp. 1776-1782
Citations number
28
Language
INGLESE
art.tipo
Article
Categorie Soggetti
Organic Chemistry/Polymer Science
Journal title
ORGANOMETALLICS
ISSN journal
0276-7333 → ACNP
Volume
20
Issue
9
Year of publication
2001
Pages
1776 - 1782
Database
ISI
SICI code
0276-7333(20010430)20:9<1776:SBCAT>2.0.ZU;2-J
Abstract
In contrast to trans-[IrCl(C2H4)(SbiPr(3))(2)] (2), which has been obtained from [IrCl(C2H4)(2)-(SbiPr(3))(2)] ii! by abstraction-of ethene together w ith some byproducts, the corresponding cycloocteneiridium(I) complex trans- [IrCl(C8H14)SbiPr(3))(2)] (4) can be prepared from [IrCl-(C8H14)(2)](2) (3) and 4 equiv of SbiPr(3) in excellent yield. Compound 4 rearranges in hexan e at room temperature to anti,exo-[IrHCl(eta (3)-C8H13)(SbiPr(3))(2)] (5a), which in benzene is in equilibrium with the anti,cndo isomer 5b. Compound 5a is generated from 4 even in the solid state. Treatment of 4 with propene and l-hexene results in the displacement, of cyclooctene and affords exo-[ IrHCl(eta (3)-C3H5)(SbiPr(3))(2)] (6a) and anti, exo- [IrHCl(eta (3)-C6H11) -(SbiPr(3)2)] (7), (7), respectively. Similarly to 5a, also 6a isomerizes t o endo-[IrHCl(eta (3)-C3H5)- (SbiPrO(3))(2)] (6b). The reaction of 6a with HCl leads to the formation of [IrHCl2(SbiPr(3))(2)]) (8), which forms the 1 :1 adduct 9 with C2H3 The preparation of other bis(triisopropylstibine)-iri dium complexes 10-12 has been achieved by using 4 as the starting material. Compounds Sa and 6a have been characterized crystallographically.