Related Experiment Video
Updated: Jun 19, 2026

Functionalization of Single-walled Carbon Nanotubes with Thermo-reversible Block Copolymers and Characterization by Small-angle Neutron Scattering
Published on: June 1, 2016
Atomic carbon as a terminal ligand: studies of a carbidomolybdenum anion featuring solid-state (13)C NMR data and
J B Greco1, J C Peters, T A Baker
1Departments of Chemistry, Massachusetts Institute of Technology, 77 Massachusetts Ave., Cambridge, Massachusetts 02139-4307, USA.
Abstract:
Anion [CMo(N[R]Ar)(3)](-) (R = C(CD(3))(2)CH(3) or (t)Bu, Ar = 3,5-C(6)H(3)Me(2)) containing one-coordinate carbon as a terminal substituent and related molecules have been studied by single-crystal X-ray crystallography, solution and solid-state (13)C NMR spectroscopy, and density functional theory (DFT) calculations. Chemical reactivity patterns for [CMo(N[R]Ar)(3)](-) have been investigated, including the kinetics of proton-transfer self-exchange involving HCMo(N[R]Ar)(3), the carbidomolybdenum anion's conjugate acid. While the Mo triple bond C bond lengths in [K(benzo-15-crown-5)(2)][CMo(N[R]Ar)(3)] and the parent methylidyne, HCMo(N[R]Ar)(3), are statistically identical, the carbide chemical shift of delta 501 ppm is much larger than the delta 282 ppm shift for the methylidyne. Solid-state (13)C NMR studies show the carbide to have a much larger chemical shift anisotropy (CSA, 806 ppm) and smaller (95)Mo--(13)C coupling constant (60 Hz) than the methylidyne (CSA = 447 ppm, (1)J(MoC) = 130 Hz). DFT calculations on model compounds indicate also that there is an increasing MoC overlap population on going from the methylidyne to the terminal carbide. The pK(a) of methylidyne HCMo(N[R]Ar)(3) is approximately 30 in THF solution. Methylidyne HCMo(N[R]Ar)(3) and carbide [CMo(N[R]Ar)(3)](-) undergo extremely rapid proton-transfer self-exchange reactions in THF, with k = 7 x 10(6) M(-1) s(-1). Besides being a strong reducing agent, carbide [CMo(N[R]Ar)(3)](-) reacts as a nucleophile with elemental chalcogens to form carbon-chalcogen bonds and likewise reacts with PCl(3) to furnish a carbon-phosphorus bond.
Related Concept Videos
Carbon-13 (¹³C) NMR: Overview
NMR Spectroscopy: Spin–Spin Coupling
Spin–Spin Coupling Constant: Overview
Qualitatively, any spin plus-half nucleus polarizes the spins of its electrons to the minus-half state. Consequently, the paired electron in the hydrogen–carbon bond must have a...
Spin–Spin Coupling: One-Bond Coupling
¹H NMR: Long-Range Coupling
In alkenes, spin information is communicated via σ–π overlap, as seen in allylic (four-bond) and homoallylic (five-bond) couplings. These coupling interactions are stronger when the σ bond is parallel to the alkene π orbitals.
¹³C NMR: ¹H–¹³C Decoupling
A broadband decoupling technique is used to simplify these complex, sometimes overlapping, signals. Broadband decoupling relies on a...

