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A complex with nitrogen single, double, and triple bonds to the same chromium atom: synthesis, structure, and reactivity.

ABSTRACT: A nitrogen-based analogue of the Schrock and Clark "yl-ene-yne" complex, W(CBu ^t )(CHBu ^t )(CH₂Bu ^t )(dmpe), has been prepared. The new complex is the nitrido, imido, amido anion [NCr(NPh)(NPrⁱ₂)₂]^-, which was structurally characterized with the [K(crypt-2.2.2)]⁺ counterion. The "Cr-N 1-2-3" complex was prepared from NCr(NHPh)(NPrⁱ₂)₂, which exists as this nitrido-amido tautomer, rather than the bis(imido) Cr(NH)(NPh)(NPrⁱ₂)₂. By selection of electrophile, the nitrido-imido salt K[NCr(NPh)(NPrⁱ₂)₂] can undergo reaction at either the imido or the nitrido to form unusual examples of nitrido or bis(imido) complexes.

SUBMITTER: Beaumier EP

PROVIDER: S-EPMC5477034 | biostudies-literature | 2016 Apr

REPOSITORIES: biostudies-literature

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A complex with nitrogen single, double, and triple bonds to the same chromium atom: synthesis, structure, and reactivity.

Beaumier Evan P EP Billow Brennan S BS Singh Amrendra K AK Biros Shannon M SM Odom Aaron L AL

Chemical science 20160113 4

A nitrogen-based analogue of the Schrock and Clark "yl-ene-yne" complex, W(CBu t )(CHBu t )(CH2Bu t )(dmpe), has been prepared. The new complex is the nitrido, imido, amido anion [NCr(NPh)(NPri2)2]-, which was structurally characterized with the [K(crypt-2.2.2)]+ counterion. The "Cr-N 1-2-3" complex was prepared from NCr(NHPh)(NPri2)2, which exi ...[more]

PMID: 28660023

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Project description:Metal complexes bearing nitrido ligands (M≡N) are at the forefront of current scientific research due to their resemblances with the metal complexes involved in the nitrogen fixation reactions. An oxo(corrolato)chromium(V) complex was used as a precursor complex for the facile synthesis of a new nitrido(corrolato)chromium(V) complex. The nitrido(corrolato)chromium(V) complex was characterized by various spectroscopic techniques. Density functional theory (DFT) calculations were performed on the nitrido(corrolato)chromium(V) complex to assign the vibrational and electronic transitions of this complex. The chromium-nitrogen (nitrido) bond distance obtained in the DFT-optimized structure is 1.530 Å and matches well with the earlier reported authentic Cr≡N bond distances obtained from the single-crystal X-ray diffraction data. This nitrido(corrolato)chromium(V) compound exhibited a sharp Soret band at 438 nm and a Q band at 608 nm. DFT calculations deliver that the origin of the bands at 438 and 608 nm is due to the intraligand charge transfer transitions. The nitrido(corrolato)chromium(V) complex showed one reversible oxidation and one reversible reduction couple at +0.53 and -0.06 V, respectively, vs the Ag/AgCl reference electrode. The simulation of the electron paramagnetic resonance data of the nitrido(corrolato)chromium(V) compound provided the following parameters: g iso = 1.987, A 53Cr = 26 G, and A 14N = 2.71 G. From all these analyses, we can conclude that the electronic configuration in the native state of nitrido(corrolato)chromium(V) can be best described as [(cor3-)CrV(N3-)]-. Reactions of nitrido(corrolato)chromium(V) with the chloro(porphyrinato)chromium(III) complex resulted in a complete intermetal N atom transfer reaction between chromium corrole and chromium porphyrin complexes. A second-order rate constant of 4.29 ± 0.10 M-1 s-1 was obtained for this reaction. It was also proposed that this reaction proceeds via a bimetallic μ-nitrido intermediate.

Dataset Information

A complex with nitrogen single, double, and triple bonds to the same chromium atom: synthesis, structure, and reactivity.

Publications

A complex with nitrogen single, double, and triple bonds to the same chromium atom: synthesis, structure, and reactivity.

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