Photochemical properties of the cyclopentadienyl(.eta.6-benzene)ruthenium(II) cation. The synthesis and reactions of a synthetically useful intermediate: the cyclopentadienyltris(acetonitrile)ruthenium(II) cation

Abstract

Photolysis of RuCp(benzene)+ in CH&N at 313 nm gives a quantitative yield of [RuCp(CH,CN),]: which is isolated as the PF6-salt. The quantum yield for this reaction is 0.4 f 0.04. The thermal substitution chemistry of this complex is remarkably rich. When the reaction conditions are varied (temperature and solvent), one, two, or three of the CH&N molecules can be selectively replaced. For example, with P(OCH3), as the incoming ligand, reaction of [RUC~(CH&N)~]PF~ with an excess of P(OCH,), in acetonitrile at room temperature gives a quantitative yield of [RUC~(CH&N)~(P(OCH,)~)]PF~. Further treatment of this monophosphite complex with an excess of P(OCH,), for several days at room temperature yields quantitatively [RuCp(CH3CN)(P(OCH3),),]PF6. Finally, refluxing this bisphosphite complex with an excess of P(OCH3)3 for several hours in dichloroethane yields [ R U C~( P ( O C H~)~)~] P F~. [CpRu(CH,CN),]+ also reacts with a variety of unsaturated hydrocarbons to yield compounds in which all three acetonitrile molecules have been replaced. Compounds synthesized by this method include: [CpRu(q6-hexamethylbenzene)]PF6, [CpRu(q6-[2.2]-p-cyclophane)]PF6, [CpRu(~f-p-dichlorobenzene)]PF~, and [CpRu(q6-cyclooctatetraene)]PFs.

Efficient Synthesis of Tris(acetonitrile)‐(η5‐cyclopentadienyl)‐ ruthenium(II) Hexafluorophosphate via Ruthenocene

“…The resulting mixture was thoroughly mixed for 5 min, the aqueous phase was separated, and the organic phase extracted with small portions of water. Addition of KPF 6 [10,12] The naphthalene complex 4 (13.7 mmol, 6 g) was placed in a Schlenk tube (200 mL) equipped with a magnetic stirring bar. Dry, N 2 -saturated acetonitrile (60 mL) was added under N 2 .…”

“…[1,7] Further applications of cationic RuCp complexes are in the fields of planar chiral Ru-arene complexes [8] and Ru-Lewis acid catalysts. [9] With much useful chemistry firmly established, it is surprising that until very recently, the best route of access to 1 was the three-step procedure first described by Gill and Mann [10] and based on the substitution of chloride in [(Ru(C 6 H 6 )Cl 2 ] 2 [11] by cyclopentadienide using TlCp followed by photolytic Ru-arene bond cleavage (Scheme 1).…”

“…Synthesis of 1 via the Gill and Mann procedure. [10] Scheme 2. Improved protocol for the synthesis of 3 according to Trost and Older. Ru(arene)Cp þ complexes.…”

A Density Functional Theory Investigation on Intramolecular Hydrogen Transfer of the [Os3(CO)11P(OMe)3(Ru(η5-C5H5))2] Cluster

“…[5][6][7][8] An efficient pathway to build nuclearity clusters is the reduction of the parent cluster with subsequent ionic coupling between the parent cluster anion and a suitable cationic capping complex. The cationic capping species such as Ru(η 12 which are isolobal to the [M(CO)3] fragment, 13 have been reacted effectively with anionic cluster compounds to build the higher nuclearity clusters. The reaction between [Os 3 (CO) 11 8 By using the empirical 18 electron rule, the structure of [Os3(CO)11P(OMe)3(Ru(η 5 -C5H5))2] was predicted to be square-base pyramidal from the total electron count of 74.…”

Modular Synthesis of Ruthenium‐Labeled Diaryl Ether Peptoids

“…As h 5 -ligand, Cp* was chosen instead of Cp because [RuCp*(h 6 -arene)] + complexes can be assembled in a one-pot procedure starting from RuCl 3 ·x H 2 O, [13] whereas the analogous Cp complexes require a four-step sequence. [14] As building blocks of the target tetrapeptoid 7 we used N-Boc-OBn-tyrosine (1), [RuCp*] + -complexed p-chlorophenylethylamine (2), tyramine (4), and the [RuCp*]…”