Solid–State Molecular Organometallic Catalysis in Gas/Solid Flow (Flow-SMOM) as Demonstrated by Efficient Room Temperature and Pressure 1-Butene Isomerization

[Image: see text] The use of solid–state molecular organometallic chemistry (SMOM–chem) to promote the efficient double bond isomerization of 1-butene to 2-butenes under flow–reactor conditions is reported. Single crystalline catalysts based upon the σ-alkane complexes [Rh(R(2)PCH(2)CH(2)PR(2))(η(2)η(2)-NBA)][BAr(F)(4)] (R = Cy, (t)Bu; NBA = norbornane; Ar(F) = 3,5-(CF(3))(2)C(6)H(3)) are prepared by hydrogenation of a norbornadiene precursor. For the (t)Bu-substituted system this results in the loss of long-range order, which can be re-established by addition of 1-butene to the material to form a mixture of [Rh((t)Bu(2)PCH(2)CH(2)P(t)Bu(2))(cis-2-butene)][BAr(F)(4)] and [Rh((t)Bu(2)PCH(2)CH(2)P(t)Bu(2))(1-butene)][BAr(F)(4)], in an order/disorder/order phase change. Deployment under flow-reactor conditions results in very different on-stream stabilities. With R = Cy rapid deactivation (3 h) to the butadiene complex occurs, [Rh(Cy(2)PCH(2)CH(2)PCy(2))(butadiene)][BAr(F)(4)], which can be reactivated by simple addition of H(2). While the equivalent butadiene complex does not form with R = (t)Bu at 298 K and on-stream conversion is retained up to 90 h, deactivation is suggested to occur via loss of crystallinity of the SMOM catalyst. Both systems operate under the industrially relevant conditions of an isobutene co-feed. cis:trans selectivites for 2-butene are biased in favor of cis for the (t)Bu system and are more leveled for Cy.