Titanium Imido Complexes by Displacement of –SiMe<sub>3</sub> and C–H Bond Activation in a Ti<sup>III</sup> Amido Complex, Promoted by a Cyclic (Alkyl)(Amino) Carbene (cAAC)

Ye, Qing; Ziegler, Micah S.; Lakshmi, K. V.; Tilley, T. Don

doi:10.1002/ejic.201700295

Cited by 5 publications

(1 citation statement)

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“…On the other hand, a short Ti–N bond with a length of 1.761(3) Å is determined, which is smaller than the calculated Ti–N single bond lengths within TiM 2 N@C 80 (M = Sc, Y) NCFs. , Interestingly, the determined Ti–N bond length is comparable to those of the TiN double bonds reported in conventional Ti-containing complexes (Table ). − Therefore, both TiN and CeN double bonds exist within TiCeN@ C 1 (12)-C 84 , fulfilling costabilization of transition metal–nitrogen and lanthanide-nitrogen double bonds bridged by nitrogen for the first time.…”

Section: Results and Discussionmentioning

confidence: 99%

Transition Metal/Lanthanide-Nitrogen Double Bonds Co-stabilized in a Carbon Cage

Jiang,

Hu,

Yao

et al. 2024

Precision Chemistry

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Metal−nitrogen double bonds have been commonly reported for conventional metal complexes, but the coexistence of both transition metal−nitrogen and lanthanide−nitrogen double bonds bridged by nitrogen within one compound has never been reported. Herein, by encapsulating a ternary transition metallanthanide heteronuclear dimetallic nitride into a C 84 fullerene cage, transition metal−nitrogen and lanthanide-nitrogen double bonds are costabilized simultaneously within the as-formed clusterfullerene TiCeN@C 1 (12)-C 84 , which is a representative heteronuclear dimetallic nitride clusterfullerene. Its molecular structure was unambiguously determined by single-crystal X-ray diffraction, revealing a slightly bent μ 2 -bridged nitride cluster with short Ti−N (1.761 Å) and Ce−N (2.109 Å) bond lengths, which are comparable to the corresponding Ti�N and Ce�N double bonds of reported metal complexes and consistent with the theoretically predicted values, confirming their coexistence within TiCeN@ C 1 (12)-C 84 . Density functional theory (DFT) calculations unveil three-center two-electron (3c-2e) bonds delocalized over the entire TiCeN cluster, which are responsible for costabilization of Ti�N and Ce�N double bonds. An electronic configuration of Ti 4+ Ce 3+ N 3− @C 84 4− is proposed featuring an intramolecular four-electron transfer, drastically different from the analogous actinide dimetallic nitride clusterfullerene (U 2 ) 9+ N 3− @C 80 6− and trimetallic nitride clusterfullerene (Sc 2 ) 6+ Ti 3+ N 3− @C 80 6−, indicating the peculiarity of 4-fold negatively charged fullerene cage in stabilizing the heteronuclear dimetallic nitride cluster.

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