191853-32-4

Upstream product

• 829-85-6 diphenylphosphane 
• 64-17-5 ethanol 
• 191853-31-3 Ru(η⁵-Cp*)Cl(PPh₂H)(PPh₃) 
• 87640-46-8 (η5-C5Me5)Ru(norbornadiene)Cl 
• 92361-49-4 pentamethylcyclopentadienyl bis(triphenylphosphine)ruthenium(II) chloride 
• 96503-27-4 pentamethylcyclopentadienylruthenium dichloride 
• 92390-26-6 chloro(1,5-cyclooctadiene)(pentamethylcyclopentadiene)ruthenium(II) 

Downstream Products

• 225670-23-5 (C₅(CH₃)5)RuCl(PCl(C₆H₅)2)2 
• 246265-64-5 (C₅(CH₃)5)RuCl(PH(C₆H₅)2)(PCl(C₆H₅)2) 
• 246265-74-7 (C₅(CH₃)5)Ru(PH(C₆H₅)2)2(CH₃CN)⁽¹⁺⁾*O₃SCF₃^(1-)=[(C₅(CH₃)5)Ru(PH(C₆H₅)2)2(CH₃CN)]O₃SCF₃ 
• 246265-69-0 (C₅(CH₃)5)Ru(P(OC₂H₅)(C₆H₅)2)2Cl 

Relevant academic research and scientific papers

Terminal Phosphido Complexes of the Ru(n5-Cp?) Fragment

In situ generation of the five-coordinate complex Ru(n5-Cp?)(PR2)(PPh3) (2), via dehydrohalogenation of Ru(n5-Cp?)Cl(PR2H)(PPh3), has allowed its reactivity toward a range of small molecules to be compared with that of its well-studied analogue Ru(n5-indenyl)(PR2)(PPh3) (1), in a study designed to assess the likelihood of variable hapticity in the chemistry of complex 1. Reactions of 2 with hydrogen, carbon monoxide, phenylacetylene, ethylene, acrylonitrile, and 1-hexene demonstrate enhanced nucleophilicity/basicity of the terminal phosphido ligand in 2 relative to that in complex 1. Complex 2 also exhibits greater lability of the PPh3 ligand, leading to substitutional product mixtures that were not observed for 1. Both of these features are consistent with the more electron-rich and sterically imposing nature of the Cp? ligand in 2 relative to the indenyl ligand in 1. Nevertheless, the fundamental transformations of the phosphido ligand are comparable for the two complexes. This suggests that variable hapticity does not play a role in reactions of indenyl complex 1, since n5-n3 shifts are unlikely to occur for Cp? complex 2. The implications of these reactivity studies for the design of highly active, yet stable, ruthenium half-sandwich catalysts for hydrophosphination are discussed.

Investigation of the reactivity of the phosphorus-hydrogen bond in Cp′RuL1L2Cl complexes with diphenylphosphine ligands

Products resulting from the oxidation, chlorination, hydrolysis and ethanolysis of Cp*Ru(PHPh2)2Cl (1) are described. Chlorination of the P-H bond in 1 allowed isolation of Cp*Ru(PClPh2)2Cl (6) and there is spectroscopic evidence for the presence of Cp*Ru(PClPh2)(PHPh2)Cl (5). Hydrolysis of compounds 1 and 5 gave a dihydride complex [Cp*Ru(H)2(OPPh2)(POHPh2)] (13) and cationic species [Cp*Ru(PHPh2)3]Cl (14) and [Cp*RuPOHPh2(PHPh2)2]Cl (15). Formation of 14 was confirmed by the synthesis of [Cp*Ru(PHPh2)3]OTf (14′) through intermediate [Cp*Ru(MeCN)(PHPh2)2]OTf (16) which was obtained from the addition of AgOTf to 1 in MeCN solution. Reaction of (Cp*RuCl2)2 (12) in EtOH with two equivalents of PHPh2 gave compound 1 and ethanolysis products Cp*Ru(POEtPh2)(PHPh2)Cl (18) and Cp*Ru(POEtPh2)2Cl (11), while reaction of 12 with diphenylphosphine oxide (OPHPh2) led to the formation of Cp*Ru(POHPh2)2Cl (7), which can either be converted to hydride compound Cp*Ru(H)(Cl)[(OPPh2)(POHPh2)] (10) or an aromatic ring of its coordinated phosphine will bind to the electrophilic [Cp*Ru]+ fragment to give compound [Cp*Ru[μ-(η6-C6H 5)POHPh]Cp*Ru(POHPh2)Cl]Cl (8). Based on 1H- and 31P-NMR spectroscopic data, compounds with two different P-donor ligands have also been prepared, including Cp*Ru(POHPh2)(PHPh2)Cl (9), [Cp*Ru(POHPh2)2(PHPh2)]OTf (17) and Cp*Ru(POHPh2)(POEtPh2)Cl (19). According to NMR observations, a free radical mechanism is proposed for the chlorination and oxidation reactions. Crystal structures are provided for complexes 6, 13 and 18, and a related cationic Cp complex [CpRu(POHPh2)(PHPh2)2]Cl (20).

Synthesis, properties and crystal structures of pentamethylcyclopentadienyl- and cyclopentadienyl-ruthenium(II) diphenylphosphine complexes

The synthesis, characterization and single-crystal structure determination of chiral compounds (η5-C5R5)Ru(PHPh2)(PPh3)Cl (R=H 3, R=Me 4) and prochiral Cp * Ru(PHPh2)2Cl (6) are described. Compound 6 has been available from reaction of PHPh2 and several starting materials. The X-ray structure comparison between 3, 4 and 6 allowed us to compare the influence of the phosphine, Cp and Cp * ligands in these half-sandwich compounds. In addition, a structural investigation was carried out on Cp * Ru(NBD)Cl (7).