1552-12-1Relevant articles and documents
Inverse Isotope Effects in Single-Crystal to Single-Crystal Reactivity and the Isolation of a Rhodium Cyclooctane σ-Alkane Complex
Doyle, Laurence R.,Furfari, Samantha K.,Galpin, Martin R.,Hicks, Scott A.,Lloyd-Jones, Guy C.,MacGregor, Stuart A.,Martínez-Martínez, Antonio J.,Tegner, Bengt E.,Weller, Andrew S.,Whitwood, Adrian C.
supporting information, p. 284 - 292 (2022/02/10)
The sequential solid/gas single-crystal to single-crystal reaction of [Rh(Cy2P(CH2)3PCy2)(COD)][BArF4] (COD = cyclooctadiene) with H2 or D2 was followed in situ by solid-state 31P{1H} NMR spectroscopy (SSNMR) and ex situ by solution quenching and GC-MS. This was quantified using a two-step Johnson-Mehl-Avrami-Kologoromov (JMAK) model that revealed an inverse isotope effect for the second addition of H2, that forms a σ-alkane complex [Rh(Cy2P(CH2)3PCy2)(COA)][BArF4]. Using D2, a temporal window is determined in which a structural solution for this σ-alkane complex is possible, which reveals an η2,η2-binding mode to the Rh(I) center, as supported by periodic density functional theory (DFT) calculations. Extensive H/D exchange occurs during the addition of D2, as promoted by the solid-state microenvironment.
Guanidinato complexes of iridium: Ligand-donor strength, O2 reactivity, and (alkene)peroxoiridium(III) intermediates
Kelley, Matthew R.,Rohde, Jan-Uwe
, p. 2564 - 2580 (2013/04/10)
A series of seven [Ir{ArNC(NR2)NAr}(cod)] complexes (1a-1g; where R = Me or Et; Ar = Ph, 4-MeC6H4, 4-MeOC 6H4, 2,6-Me2C6H3, or 2,6-iPr2C6H3; and cod = 1,5-cyclooctadiene) were synthesized by two different methods from the neutral guanidines, ArN-C(NR2)NHAr, using either MeLi and [{Ir(cod)} 2(μ-Cl)2] or [{Ir(cod)}2(μ-OMe) 2]. Reaction of 1a-1g with CO produced the corresponding [Ir{ArNC(NR2)NAr}(CO)2] complexes (2a-2g), which were characterized by NMR and solution- and solid-state IR spectroscopy. Complexes 1b (R = Et, Ar = Ph), 1d (R = Et, Ar = 4-MeC6H4), 1f (R = Me, Ar = 2,6-Me2C6H3), and 2b (R = Et, Ar = Ph) were characterized by X-ray crystallography as mononuclear complexes with a guanidinato-κ2N,N′ ligand and a cod or two CO ligands coordinated to the Ir center in a distorted square-planar environment. On the basis of the CO stretching frequencies of 2a-2g [avg. νCO (n-pentane) = 2016-2019 cm-1] and the alkene 13C chemical shifts of 1a-1g [δ(13CC-C) = 58.7-61.0 ppm], the donor strength of the guanidinato ligands was evaluated and compared to that of related monoanionic ligands. Reaction of 1a-1g in solution with O2 at 20 C afforded (alkene)peroxoiridium(III) intermediates, [Ir{ArNC(NR 2)NAr}(cod)(O2)] (3). The steric properties of the supporting ligand play a decisive role in O2 binding in that complexes without ortho substituents react largely irreversibly with O 2 (1a-1e; where Ar = Ph, 4-MeC6H4 or 4-MeOC6H4), whereas complexes with ortho substituents exhibit fully reversible O2 binding (1f and 1g; where Ar = 2,6-Me2C6H3 or 2,6-iPr 2C6H3). Complexes 3a-3f were characterized by 1H NMR and IR spectroscopy (νOO = 857-872 cm -1). Decay of the new intermediates and subsequent reaction with cod produced 4-cycloocten-1-one and the respective IrI precursor.
PROCESS FOR PRODUCING HIGH PURITY EXO-ALKENYLNORBORNENE
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Page/Page column 12, (2009/07/02)
Embodiments of the present invention are directed generally to methods for producing high purity exo-alkenylnorbornenes from a mixture of conformational isomers thereof.
