Reactions of the first-generation Grubbs’ catalyst trans-[RuCl₂(CHPh)(PCy₃)₂] (1) with the amidinatogermylenes Ge(^tBu₂bzam)R (R = ^tBu (L¹), CH₂SiMe₃ (L²); ^tBu₂bzam = N,N′-bis(tertbutyl)benzamidinate) have allowed the isolation and full characterization of the first specimens of Grubbs-type carbene complexes featuring heavier tetrylenes as ancillary ligands, namely, the disubstituted derivatives trans-[RuCl₂(CHPh)(L¹)₂] (3) and cis-[RuCl₂(CHPh)(L²)₂] (7), which curiously differ in the arrangement of their germylene ligands. DFT calculations have revealed that the different volumes of L¹ and L² (the former is larger than the latter) are responsible for the different stereochemistry of 3 and 7. NMR-monitoring of the reaction solutions has allowed the observation of the monosubstituted intermediates trans-[RuCl₂(CHPh)(L)(PCy₃)] (L = L¹ (2), L² (5)) and their evolution to either the disubstituted final product (for L¹) trans-[RuCl₂(CHPh)(L¹)₂] (3) or the short-lived disubstituted intermediate (for L²) trans-[RuCl₂(CHPh)(L²)₂] (6). Complex 7 arises from a trans-to-cis isomerization of intermediate 6. As olefin metathesis catalysts, both 3 and 7 promoted the ring-closing metathesis of diethyl 2,2-diallylmalonate and the ring-opening metathesis polymerization of norbornene, but their catalytic activity decreased with the reaction time, indicating catalyst decomposition.

中文翻译：

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与Grubbs-I催化剂类似的钌碳烯络合物，其特征在于亚甲基苯作为辅助配体

第一代Grubbs催化剂反式-[RuCl ₂（CHPh）（PCy ₃）₂ ]（1）与mid基亚锗烷基Ge（^t Bu ₂ bzam）R（R = ^t Bu（L ¹），CH ₂ SiMe的反应₃（L ²）; ^t Bu ₂ bzam = N，N'-双（叔丁基）苯甲mid酸酯）可以分离并完全表征Grubbs型卡宾配合物的第一批样品，其特征是较重的四甲苯为辅助配体，即二取代的衍生品反式[RuCl ₂（CHPh）（L ¹）₂ ]（3）和顺式[RuCl ₂（CHPh）（L ²）₂ ]（7），它们的亚甲基配体的排列奇怪地不同。DFT计算表明，L ¹和L ^2的体积不同（前者大于后者）是造成3和7立体化学差异的原因。反应溶液的NMR监测可以观察到反式的单取代中间体-将[RuCl ₂（CHPh配合）（L）（PCY ₃）]（L =大号¹（2），大号²（5））和它们的演进无论是二取代最终产物（对于大号¹）反式-将[RuCl ₂（ CHPh）（L ¹）₂ ]（3）或短寿命的双取代中间体（对于L ²）反式-[RuCl ₂（CHPh）（L ²）₂ ]（6）。复合物7来自反式-到-顺式的异构中间体6。作为烯烃复分解催化剂，3和7都促进了2,2-二烯丙基丙二酸二乙酯的闭环复分解和降冰片烯的开环复分解聚合，但它们的催化活性随反应时间的延长而降低，表明催化剂分解。