Structure, Dynamic Behavior, and Catalytic Activity of a Novel Ruthenium Cyclopentadienyl Complex with a Tridentate P,P,O Ligand

Reaction of 1,2-bis(bis(o-methoxyphenyl)phosphino)ethane (o-MeO-dppe) with [RuClCp(PPh3)2] (1) at 135 °C results in the formation of (η5-cyclopentadienyl)[1-(bis(o-methoxyphenyl)phosphino-κP)-2-((o-methoxyphenyl)(o-phenolato-κO)phosphino-κP)ethane]ruthenium(II) ([RuCp(tappe)]; 3), which constitutes the first example of a ruthenium cyclopentadienyl
complex with a tridentate P,P,O ligand. The X-ray structure of 3 has been determined to
elucidate its solid-state structure, which shows evidence for a CH/π interaction. An NMR
study corroborates this finding, and temperature-dependent 31P and 1H NMR spectra reveal
the dynamic behavior of 3 in solution. Complex 3 shows catalytic activity in the isomerization
of allylic alcohols to carbonyl compounds.

135°C下，1,2-双(对-甲氧基苯基)膦基乙烷(o-MeO-dppe)与[RuClCp(PPh3)2](1)的反应生成(η5-环戊二烯基)[1-(双(对-甲氧基苯基)膦基-κP)-2-((对-甲氧基苯基)(对-苯酚酸根-κO)膦基-κP)乙烷]钌(II)([RuCp(tappe)]); 3)，此化合物为首个具有三齿P,P,O配体的钌环戊二烯基络合物的实例。3的X射线晶体结构分析揭示了其固态结构，并证实了C-H/π相互作用的证据。核磁共振(NMR)研究进一步验证了这一发现，温度依赖性31P和1H NMR光谱揭示了3在溶液中的动态行为。络合物3在烯丙醇异构化生成羰基化合物方面展现出催化活性。