Compound 3a showed excellent herbicidal activity against barnyard grass with IC ₅₀ = 7.0 mg L ⁻¹ , and exhibited good selection for rice, wheat, and radish at 100 mg L ⁻¹ .

In this study, a series of novel sec-p-menthane-7-amine derivatives were designed, synthesized, and evaluated to be used as efficient botanical herbicides owing to their post-emergence herbicidal activities against barnyard grass and rape.

Selective aerobic oxidation of α-pinene to high-value products is a major challenge in chemistry. Metalloporphyrins are proved to be selective catalysts for aerobic oxidation of simple hydrocarbons. Herein, we extend this method to more complex substrates using metallodeuteroporphyrins as model catalysts. It was found that the oxidation occurs mainly on the C=C and allylic C–H bonds of α-pinene influenced by the reaction temperature, reaction time, catalyst concentration, and oxygen flow rate. Allylic C–H oxidation products are obtained with a maximum selectivity value of 78.4% using the following reaction conditions: 105°C, 7 h, 5 ppm, and 60 mL/min. The influence of the metal nuclei of the metallodeuteroporphyrins on this reaction is also investigated. It was found that metallodeuteroporphyrins with Fe³⁺ as the metal nucleus exhibit the highest catalytic activity.

Using backbone modification of popular β-diketiminate ligands, ^RDipnacnac = HC­(RCNDip)₂, with R = Et, iPr (Dip = 2,6-iPr₂C₆H₃), we have prepared the new β-diketiminate gallium­(I) complexes [(^EtDipnacnac)­Ga] 2a and [( ^iPrDipnacnac)­Ga] 2b by salt metathesis/reduction using “GaI” in moderate to good (68%, 2a) and poor (10%, 2b) isolated yields, respectively, highlighting the influence of the ligand backbone substitution on the reaction success. The gallium­(I) complexes were converted with azobenzene to the gallium­(III) complexes [(^RDipnacnac)­Ga­{(C₆H₅)­NNPh}] 4a (R = Et) and 4b (R = iPr) with reduced former azobenzene fragments showing an N,ortho-C­(H)-chelating coordination to the Ga centers. Complex 4a was further converted to its C–H-activated tautomer [(^EtDipnacnac)­Ga­{(C₆H₄)­N­(H)­NPh}] 5, and reaction with DMSO and benzaldehyde afforded [(^EtDipnacnac)­Ga­(PhNNHPh)­(CH₂S­(O)­Me)] 6 after DMSO deprotonation and [(^EtDipnacnac)­Ga­(PhNN­(Ph)­CH­(Ph)­O)] 7 from C–N coupling, respectively. Compound 2a also reacted with the aluminum­(III) hydride complexes (NHC)­AlH₃ (NHC = {MeCN­(iPr)}₂C) and (Me₃N)­AlH₃ to the Ga–Al-bonded complex [(^EtDipnacnac)­Ga­(H)–Al­(H₂)­(NHC)] 8 and [(^EtDipnacnac)­GaH₂] 9, respectively. Gallium­(I) complex 2a is a good alternative to commonly used [(^MeDipnacnac)­Ga] (R = Me) for the study and application of low-oxidation-state gallium complexes.

We report the synthesis, characterisation and reactivity of the stable imidazol-2-ylidene ^EtIDip (^EtIPr), {EtCN(Dip)}₂C:, Dip = 2,6-iPr₂C₆H₃, as a chemically robust alternative to IDip (IPr), {HCN(Dip)}₂C:. The N-heterocyclic carbene ^EtIDip could be further converted to the oxidised species [^EtIDipCl]Cl, ^EtIDipF₂, ^EtIDipO, and ^EtIDipSe, and the group 13 element complexes ^EtIDipEX₃, with E = B, X = Br; E = Al, X = I; E = Ga, X = I; E = Al, X = H. The properties of the ^EtIDip and IDip ligands are compared and the molecular structures of (DipNCEt)₂, [^EtIDipH]Cl, [^EtIDipH]I, ^EtIDip, [^EtIDipCl]Cl, ^EtIDipF₂, ^EtIDipO, ^EtIDipBBr₃, ^EtIDipAlI₃, ^EtIDipGaI₃, and ^EtIDipAlH₃ have been determined.