768382-11-2Relevant academic research and scientific papers
New perspectives in hydroformylation: A para-hydrogen study
Godard, Cyril,Duckett, Simon B.,Henry, Celine,Polas, Stacey,Toose, Robert,Whitwood, Adrian C.
, p. 1826 - 1827 (2004)
NMR studies on the reaction of Ir(CO)(PPh3)2(η 3-C3H5) with para-H2 and CO enable the complete mapping of the hydroformylation mechanism for an iridium monohydride catalyst via the detection of species which include iridium acyl and alkyl dihydride intermediates.
Using: Para hydrogen induced polarization to study steps in the hydroformylation reaction
Guan, Dexin,Godard, Cyril,Polas, Stacey M.,Tooze, Robert P.,Whitwood, Adrian C.,Duckett, Simon B.
supporting information, p. 2664 - 2675 (2019/02/27)
A range of iridium complexes, Ir(η3-C3H5)(CO)(PR2R′)2 (1a-1e) [where 1a, PR2R′ = PPh3, 1b P(p-tol)3, 1c PMePh2, 1d PMe2Ph and 1e PMe3] were synthesized and their reactivity as stoichiometric hydroformylation precursors studied. Para-hydrogen assisted NMR spectroscopy detected the following intermediates: Ir(H)2(η3-C3H5)(CO)(PR2R′) (2a-e), Ir(H)2(η1-C3H5)(CO)(PR2R′)2 (4d-e), Ir(H)2(η1-C3H5)(CO)2(PR2R′) (10a-e), Ir(H)2(CO-C3H5)(CO)2(PR2R′) (11a-c), Ir(H)2(CO-C3H7)(CO)2(PR2R′) (12a-c) and Ir(H)2(CO-C3H5)(CO)(PR2R′)2 (13d-e). Some of these species exist as two geometric isomers according to their multinuclear NMR characteristics. The NMR studies suggest a role for the following 16 electron species in these reactions: Ir(η3-C3H5)(CO)(PR2R′), Ir(η1-C3H5)(CO)(PR2R′)2, Ir(η1-C3H5)(CO)2(PR2R′), Ir(CO-C3H5)(CO)2(PR2R′), Ir(CO-C3H7)(CO)2(PR2R′) and Ir(CO-C3H5)(CO)(PR2R′)2. Their role is linked to several 18 electron species in order to confirm the route by which hydroformylation and hydrogenation proceeds.
