Theoretical insights into the reaction of Cp*(Cl)Hf(diene) with isonitriles

Du, Mingran; Zhang, Xiang-Biao; Si, Sheng-Meng; Wang, Lei

doi:10.1039/c7ra08981c

Cited by 2 publications

(1 citation statement)

References 117 publications

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“…Two classes of Group 4 diene complexes, Cp*(Cl)M(diene) (M = Ti and Hf) and Cp* 2 Zr(diene), are well known, and the reactions of both with isonitriles have been examined . The RNC reactions of Cp*(Cl)M(diene) are complex, probably because their coordinative unsaturation encourages multiple insertions; the Cp* 2 Zr(diene) complexes are not only difficult to prepare but relatively slow to react with isonitriles, probably because their coordinative saturation discourages insertion.…”

Section: Introductionmentioning

confidence: 99%

Insertion of Isonitriles into the M–C Bonds of Group 4 Dialkyl Complexes

et al. 2018

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The 2,3-dimethylbutadiene complexes of Group 4 metals with constrained geometry (cg) ligands have been prepared and found to adopt a supine orientation with σ,π bonding. Treatment of cgTi(2,3-dimethylbutadiene) (1-Ti) with BuNC leads to the formation of a titana-aziridine (3) with a coordinated cyclopentenimine that arises from the formal [4+1] addition of the diene to the isonitrile. In contrast, the reactions of cgZr(2,3-dimethylbutadiene) (1-Zr) or cgHf(2,3-dimethylbutadiene) (1-Hf) with 2 equiv ofBuNC or XyNC proceeded in a more sophisticated manner to yield unsymmetrical 2,5-diazametallacyclopentane derivatives (4, 6-Zr, and 6-Hf) or symmetrical 2,5-diazametallacyclopentene complexes (7-Zr and 7-Hf). The unsymmetrical products contain coordinated cyclopropanes; the strength of the interaction is measured by the reduction in the J of the C-C bond that is coordinated. A detailed mechanistic analysis has been possible with the related cgM(Me) (M = Ti and Hf) complexes. The first insertion is too fast to monitor, but allows complete conversion to an alkyl iminoacyl intermediate. The second isonitrile (RNC) may react with that intermediate by either of two different mechanisms, reductive elimination and coordination/insertion. In the first mechanism (Ti), rate-determining C-C coupling gives a titana-aziridine, followed by fast coordination of the isonitrile. In the second mechanism (Hf), coordination is the slow step; insertion to form a bis(iminoacyl) Hf complex is rapid.

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Section: Introductionmentioning

confidence: 99%

Insertion of Isonitriles into the M–C Bonds of Group 4 Dialkyl Complexes

et al. 2018

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Rare-Earth Metallacycloheptatrienes: Synthesis, Structure, and Reactivity

Chai,

Wei,

Zhang

2023

Organometallics

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As the key intermediates in metal-catalyzed [2 + 2 + 2] cycloaddition reactions of three alkynes, main-group and transitionmetal metallacycloheptatrienes have been studied for decades, but rareearth analogues have remained illusive. Herein, we report the welldefined rare-earth metallacycloheptatrienes 2-Sc and 2-Lu obtained in high yields via the reaction of Cp*Li (Cp* = pentamethylcyclopentadienyl) and RECl 3 (RE = Sc, Lu) with TMEDA-coordinated 2,2′dilithio-Z-stilbene 1. The single-crystal structure of 2-Sc (RE = Sc) reveals it to be a separate ion pair, and the scandacycloheptatriene ring adopts a nonplanar boat-like conformation. The reactivity of compounds 2-Sc and 2-Lu has been investigated. When 2-Sc was treated with 2,6-dimethylphenyl isocyanide, compound 3 was obtained via the successive 1,1-insertion and 1,2-insertion of the isocyanide. The structure of 3 was also fully characterized.

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Theoretical insights into the reaction of Cp*(Cl)Hf(diene) with isonitriles

Abstract: The reaction of Cp*(Cl)Hf(2,3-dimethylbutadiene) with isonitriles is theoretically investigated, and detailed elementary reactions and the substitution effects are examined.

Cited by 2 publications

References 117 publications

Insertion of Isonitriles into the M–C Bonds of Group 4 Dialkyl Complexes

Insertion of Isonitriles into the M–C Bonds of Group 4 Dialkyl Complexes

Rare-Earth Metallacycloheptatrienes: Synthesis, Structure, and Reactivity

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