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Cp2Ti(?2-tBuNCNtBu): A Complex with an Unusual ?2 Coordination Mode of a Heterocumulene Featuring a Free Carbene.

ABSTRACT: Although there are myriad binding modes of heterocumulenes to metal centers, the monometallic ?2-ECE (E = O, S, NR) coordination mode has not been reported. Herein, the synthesis, isolation, and physical characterization of Cp2Ti(?2-tBuNCNtBu) (3) (Cp = cyclopentadienyl, tBu = tert-butyl), a strained 4-membered metallacycle bearing a free carbene, is described. Computational (DFT, CASSCF, QT-AIM, ELF) and solid-state CP-MAS 13C NMR spectroscopic analysis indicate that 3 is best described as a free carbene with partial Ti-C? bonding that results from Ti-N ?-bonding mixing with N-C-N ?-bonding of the bent N-C-N framework. Reactivity studies of 3 corroborate its carbene-like nature: protonation with [LutH]I results in the formation of a Ti-formamidinate (4), while oxidation with S8 yields a Ti-thioureate (5). Additionally, a related bridged dititanamidocarbene, (Cp2Ti)2(?-?1,?1-CyNCNCy) (10) (Cy = cyclohexyl) is reported. Taken together, this work suggests that the 2-electron reduction of heterocumulene moieties can allow access to unusual free carbene coordination geometries given the proper stabilizing coordination environment from the reducing transition metal fragment.

SUBMITTER: Beaumier EP 

PROVIDER: S-EPMC7201867 | biostudies-literature | 2020 Apr

REPOSITORIES: biostudies-literature

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Cp<sub>2</sub>Ti(κ<sup>2</sup><i>-</i><sup><i>t</i></sup>BuNCN<sup><i>t</i></sup>Bu): A Complex with an Unusual κ<sup>2</sup> Coordination Mode of a Heterocumulene Featuring a Free Carbene.

Beaumier Evan P EP   Gordon Christopher P CP   Harkins Robin P RP   McGreal Meghan E ME   Wen Xuelan X   Copéret Christophe C   Goodpaster Jason D JD   Tonks Ian A IA  

Journal of the American Chemical Society 20200415 17

Although there are myriad binding modes of heterocumulenes to metal centers, the monometallic κ<sup>2</sup>-ECE (E = O, S, NR) coordination mode has not been reported. Herein, the synthesis, isolation, and physical characterization of Cp<sub>2</sub>Ti(κ<sup>2</sup>-<sup><i>t</i></sup>BuNCN<sup><i>t</i></sup>Bu) (<b>3</b>) (Cp = cyclopentadienyl, <sup><i>t</i></sup>Bu = <i>tert</i>-butyl), a strained 4-membered metallacycle bearing a free carbene, is described. Computational (DFT, CASSCF, QT-AIM,  ...[more]

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