240122-99-0

Upstream product

• 240123-01-7 (CO)2Ru(C₅H₅)(P(OC₆H₄NMe)2) 
• 240122-96-7 [(η(5)-C5H5)(CO)2Ru(P(OPh)3)]BF4 
• 95-55-6 2-amino-phenol 

Relevant academic research and scientific papers

Phosphorane Migration from Ruthenium to the Cyclopentadienyl Ring

Ruthenium phosphorane complexes, Cp(CO)2Ru{P(OC6H4Z)2} (Z = NMe, O), react with lithium diisopropylamide (LDA) to give Li[{η5-C5H4P(OC6H 4Z)2}(CO)2Ru] (5). In this reaction, one of the protons on the Cp ring is abstracted by LDA and then migration of the phosphorane fragment to the Cp ring takes place. Treatment of 5 with RX (CH3I, PhCH2Cl, Ph3SnCl, HOCOCF3, CD3I) yields {η5-C5H4P(OC6H 4Z)2}(CO)2RuR (2). The structure of one of the products, {η5-C6H4P(OC6H 4NMe)2}(CO)2RuCH2Ph, was determined by X-ray analysis. A reaction of a cationic phosphite complex, [Cp(CO)2Ru{P(OC6H4NMe)(OC6H 4NMeH)}]BF4 (6), with 2 equiv of LDA also gives 5. However, the following addition of RX at -30°C gives the unexpected phosphorane-migration complex {η5-C5H4P(OC6H 4NMe)2}(CO)2RuR, which contains one O atom and one N atom in apical positions and in equatorial positions as well. The complex gradually isomerizes to a thermally more stable apical oxygen-equatorial nitrogen isomer (2).

Syntheses, structures, and Berry pseudorotation of ruthenium-phosphorane complexes

Ruthenium complexes containing a hypervalent phosphorus ligand, [Cp(CO)2Ru{P-(OC6H4E)2}] (E = NH (2a), NMe (2b), or O (4a)), [Cp(CO)2Ru{P(OC10H6O)2}] (4b), and [Cp-(CO)2Ru{P(OC7H6O)2}] (4c), were prepared in the reaction of [Cp(CO)2Ru{P(OPh)3}]BF4 (1) with the corresponding aryl alcohol or arylamine and Et3N or n-BuLi. The comparison of spectroscopic data of [Cp(CO)2M{P(OC6H4E)2}] (M = Ru, Fe) (E = NH, NMe, O) reveals that the Ru-P bonding is more polarized as Mδ+-Pδ- than the Fe-P bonding. During the course of preparation of 2b, a phosphite complex [Cp(CO)2Ru{P(OC6H4NMe)(OC6H 4NMeH)}]-BF4 (3) was isolated, which reacted with a Lewis base to give 2b. The X-ray structures of 2b, 4b, and 3 were determined. 2b and 4b have slightly distorted trigonal-bipyramidal geometries. From the variable-temperature 31P NMR study for 4c, the activation parameters for Berry pseudorotation around the pentacoordinate phosphorus were determined to be ΔH? = 42.1 ± 0.5 kJ mol-1, ΔH? = -91.1 ± 1.6 J mol-1 K-1, and ΔG340? = 73.1 ± 0.7 kJ mol-1. This constitutes the first determined activation parameters of Berry pseudorotation for a metallaphosphorane complex.