33541-67-2Relevant articles and documents
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.
Iridium- and rhodium-silanol complexes: Synthesis and reactivity
Goikhman, Roman,Aizenberg, Michael,Shimon, Linda J.W.,Milstein, David
, p. 4020 - 4024 (2008/10/08)
Methods of metallo-silanol synthesis have been developed. The Ir(I) complex (Et3P)2Ir(C2H4)Cl (1) oxidatively adds secondary silanols R2SiHOH (R = iPr, tBu) to yield the iridium-silanol complexes [(Et3P)2Ir(H)(Cl)(SiR2OH)] (R = iPr, 2; R = tBu, 3). The crystal structure of 2 exhibits a trigonal-bipyramidal geometry, and intermolecular Si-O-H- - -Cl hydrogen bonding is present. Deprotonation of 2 results in the highly thermodynamically stable metallo-silanolate [(Et3P)2Ir(H)(Cl) (SiiPr2OLi)]2 (4). Compound 4 has an almost planar core, consisting of two atoms each of iridium, silicon, chlorine, oxygen, and lithium. Upon treatment of (Et3P)3RhCl with HSiiPr2OH, the first Rh-silanol complex, trans-[(Et3P)2Rh(H)(Cl)(iPrSi2OH)], is formed in an equilibrium with the starting complex (Keq = 4 × 10-3); hence, the reaction is dependent on the concentration of the silanol and Et3P, an excess of the latter shifting the equilibrium to the starting compounds. Reaction of the bis-phosphine complex [(Et3P)2RhCl]2 with the silanol, which does not generate free phosphine, results in 96% conversion to the adduct. On the other hand, the chelating bis-phosphine complex [(bis-(diisopropylphosphino)propane)RhCl]2 does not add the silanol even in the presence of a 10-fold excess of the silanol, indicating that the cis-phosphine configuration in the adduct is unfavorable. In contrast to the Et3P-containing Ir complex, and similarly to the Rh complex, (PPh3)3Ir(CO)H reacts with iPr2SiHOH reversibly, leading to 60% conversion to the metallosilanol (PPh3)2Ir(CO)(H)2(SiiPr2O H) (6). A stable PPh3-containing Ir-silanol was prepared by starting from (PPh3)2Ir(CO)(H)2(Si(SEt)3). Following reaction with Et3SiOSO2CF3 to exchange one SEt substituent with OSO2CF3, reaction with NaOH generates the stable silanol complex (PPh3)2Ir(CO)(H)2(Si(SEt)2OH) (14).
Decomposition of iridium alkoxide complexes trans-ROIr(CO)(PPh3)2 (R = Me, n-Pr, and l-Pr): Evidence for β-elimination
Bernard, Karen A.,Rees, Wayne M.,Atwood, Jim D.
, p. 390 - 391 (2008/10/08)
Decomposition of trans-ROIr(CO)(PPh3)2 in the presence of PPh3 leads to HIr(CO)(PPh3)3 for R = Me, n-Pr, and i-Pr. For R = H, t-Bu, or Ph, this decomposition is not observed. For R = i-Pr similar quantities of acetone and 2-propanol are observed with total yield of 90% based on starting iridium complex. Propanal is formed for R = n-Pr. The reaction between trans-i-PrOIr(CO)(PPh3)2 and HIr(CO)(PPh3)3 readily yields 2-propanol. Thus a β-hydrogen abstraction to yield organic carbonyl and HIr(CO)(PPh3)3 is indicated with 2-propanol possibly formed by a binuclear reaction between trans-i-PrOIr(CO)(PPh3)2 and HIr(CO)(PPh3)3.