Application of Ultrahigh‐Field ⁵⁹Co Solid‐State NMR Spectroscopy in the Investigation of the 1,2‐Polybutadiene Catalyst [Co(C₈H₁₃)(C₄H₆)]

Abstract

Highly suitable: The 1,2‐polybutadiene catalyst [Co(η3:η2‐C8H13)(η4‐C4H6)] (1) was isolated and structurally characterized by ultrahigh‐field 59Co solid‐state NMR spectroscopy, demonstrating the utility of this technique. It can be applied to study the formation mechanism of syndiotactic 1,2‐polybutadiene. The picture shows a QCPMG (a) and a quadrupole echo 59Co NMR spectrum (b) as well as a simulated spectrum of 1 (c).

NMR of Macromolecular Assemblies and Machines at 1 GHz and Beyond: New Transformative Opportunities for Molecular Structural Biology

“…NMR studies of inorganic materials will greatly benefit from increased magnetic field strengths as many inorganic nuclei have large quadrupolar coupling constants and/or low natural abundance. Nuclei of particular interest for inorganic applications that have been shown to benefit from higher magnetic field strengths include 6 Li (I = 1, 7.6% natural abundance (NA) (36, 37)), 11 B (I = 3/2, 80.1% NA (36, 38)), 17 O (I = 5/2, 0.04% NA (38, 39)), 25 Mg (I = 5/2, 10.0% NA (36, 38)), 27 Al (I = 5/2, 100% NA (38)), 59 Co (I = 7/2, 100% NA (40, 41)), 73 Ge (I = 9/2, 7.7% NA (42)), and 127 I (I = 5/2, 100% NA (43, 44)). These elements are essential components of materials in many fields of inorganic chemistry research, including batteries and fuel cells, semiconductors, optical materials, metal organic frameworks (MOFs), catalysts, and glasses.…”

Organometallic chemistry

“…Postdocs from all over the world studied industrially important processes focusing on their fundamental principles [110,112,115,121,123,126–127]. The biennial “Heidelberg Forum of Molecular Catalysis” (HFMC), organized by Peter Hofmann until 2013, has been one of the most visible scientific events of Heidelberg’s chemical institutes.…”

Structural Insights from 59Co Solid‐State NMR Experiments on Organocobalt(I) Catalysts

“…Additionally, dynamic nuclear polarization NMR techniques have been implemented on 59 Co using paramagnetic Cr III dopants in the hopes of increasing the sensitivity of 59 Co solid‐state NMR . For the Co I oxidation state, however, only a handful of 59 Co NMR studies exist in the literature, including that of the syndiotactic 1,2‐polybutadiene catalyst, Co(η 3 :η 2 ‐C 8 H 13 )(η 4 ‐C 4 H 6 ) in the solid state . Other studies have determined 59 Co isotropic chemical shifts, δ iso , in solution for various diamagnetic organocobalt(I) complexes and correlated this NMR parameter with the catalytic activity and product regioselectivity of the complex in cocyclization reactions …”