Reactions of gallyliron complexes Cp*(OC)₂FeGaR₂ (R = Cl (1), Mes (2); Cp*, η⁵-C₅Me₅; Mes, 2,4,6-Me₃C₆H₂) with pyridine in C₆D₆ afforded pyridine-stabilized gallyl complexes Cp*(OC)₂Fe{GaR₂(py)} (R = Cl (3), Mes (5a); py, pyridine). Photoirradiation of dichlorogallyl complex 3 in the presence of excess pyridine in benzene proceeded via the substitution of a CO ligand with another pyridine to give Cp*(OC)(py)Fe{GaCl₂(py)} (4). However, photoirradiation of dimesitylgallyl complex 2 in the presence of excess pyridine gave gallane(pyridyl)iron complex Cp*(OC)Fe{(η¹-HGaMes₂)(η¹-2-C₅H₄N)} (6a) via CO elimination and oxidative addition of the C–H bond at the 2-position of the gallium-coordinated pyridine. X-ray crystal structure analysis of 6a revealed the formation of a 3-center-2-electron (3c2e) bond in the Fe–H–GaMes₂ fragment. Reaction of 4 with methyl acrylate in toluene at 50 °C resulted in substitution of the pyridine ligand on the iron atom with the C=C bond, giving Cp*(OC)(η²-CH₂=CHCO₂Me)Fe{GaCl₂(py)} (7). In contrast, the reaction of 6a with methyl acrylate in toluene at 100 °C afforded vinyliron complex Cp*(OC)₂Fe(CH=CH₂) (8) and 4-membered Ga₂O₂ cyclic gallane compound [Mes₂GaOMe]₂ (9) via cleavage of the Fe–Ga, C–O, and C–C bonds.

中文翻译：

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Gallyliron 与吡啶配体配合物的合成和结构及其与丙烯酸甲酯的反应

gallyliron 配合物的反应 Cp*(OC) ₂ FeGaR ₂ (R = Cl ( 1 ), Mes ( 2 ); Cp*, η ⁵ -C ₅ Me ₅ ; Mes, 2,4,6-Me ₃ C ₆ H ₂ ) 与 C ₆ D _{6 中的}吡啶提供吡啶稳定的没食子络合物 Cp*(OC) ₂ Fe{GaR ₂ (py)} (R = Cl ( 3 ), Mes ( 5a ); py, 吡啶)。二氯戊二烯配合物3 的光辐照在苯中过量吡啶的存在下，通过用另一种吡啶取代 CO 配体，得到 Cp*(OC)(py)Fe{GaCl ₂ (py)} ( 4 )。然而，在过量吡啶的存在下对二甲基丙烯酰基配合物2进行光照射得到了镓 (吡啶基) 铁配合物 Cp*(OC)Fe{(η ¹ -HGaMes ₂ )(η ¹ -2-C ₅ H ₄ N)} ( 6a )通过 CO 消除和氧化加成在镓配位吡啶的 2 位上的 C-H 键。6a 的X 射线晶体结构分析揭示了在 Fe-H-GaMes _{2 中}形成了 3-center-2-electron (3c2e) 键分段。的反应4在甲苯中的丙烯酸甲酯在50℃下导致对与C = C键中的铁原子与吡啶配位体的取代，得到的Cp *（OC）（η ² -CH ₂ = CHCO ₂ Me）的铁{的GaCl ₂ (py)} ( 7 )。相比之下，6a与丙烯酸甲酯在甲苯中于 100 °C 反应得到乙烯基铁配合物 Cp*(OC) ₂ Fe(CH=CH ₂ ) ( 8 ) 和四元 Ga ₂ O ₂环镓烷化合物 [Mes ₂ GaOMe ] ₂ ( 9 ) 通过断裂 Fe-Ga、C-O 和 C-C 键。