240122-96-7

Upstream product

• 101-02-0 triphenyl phosphite 
• 14104-20-2 silver tetrafluoroborate 

Downstream Products

• 240122-99-0 [(η(5)-C5H5)(CO)2Ru(P(OC6H4NMe)(OC6H4NHMe))]BF4 

Relevant academic research and scientific papers

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.

Displacement of a cis-Olefin from a trans-Olefin Complex: CpRu(CO) 2(trans-olefin)+

Ruthenium(II) - olefin complexes CpRu(CO)2(η2- trans-olefin)+ (Cp = η2-C5H5; olefin = trans-3-hexene, trans-2-pentene, trans-3-octene, trans-4-octene, trans-5-decene) have been synthesized and characterized by IR, 1H NMR, and 13C NMR spectroscopies. The reactions of these complexes with a wide range of ligands (L) result in the formation of CpRu(CO) 2(L)+ and the release of both cis- and trans-olefins: [CpRu(CO)2(trans-olefin)]BF4 + L → [CpRu(CO) 2(L)]BF4 + cis/trans-olefin. The relative amounts of cis- and trans-olefin released are controlled by several factors: identity and amount of the incoming ligand L, identity of the olefin, temperature, and solvent. For 4-substituted pyridines, the cis/trans ratio increases as the electron-donating ability of the 4-substituent increases: F3C (18/82) 3 (74/26) 3O (76/24). Increases in temperature, solvent polarity, and olefin side-chain length reduce the cis/trans ratio. A mechanism is proposed to account for the isomerization of trans-olefin ligands to their cis isomers during the substitution process.