Preparations of Cyclopentadienylruthenium Complexes with Trimethylphosphine Ligands

Abstract

The r e a c t i o n o f R U ( C~W~) ( P P~~)~C~ w i t h PMe3 i n t h e p o l a r s o l v e n t E tOH , f o l 1 owed by metathes i s , g i ves [ Ru ( C5H5) ( PP h3) 2( PMe3) ]PF6. However i n a l e s s p o l a r s o l v e n t , toluene, t h e r e a c t i o n proceeds i n a d i f f e r e n t manner, g i v i n g Ru(C5H5)(PMe3)2C1. i n a s i m i l a r f a s h i o n t o g i v e Ru(C5H5)(dpe)C1. Ru(C5H5)(PMe3)2X ( X = Br, I , SCN), can be prepared from t h e c h l o r i d e complex by a n i o n exchange, and t h e compound w i t h X = SnC13 can be prepared by a d d i t i o n o f SnC12 t o t h i s Precursor. I o n i c complexes [ R u ( C~H~) ( P M~~)~L ] X (L = PMe3, CO, PPh3) a r e formed from Ru(C5H5)-(PMe3)2C1 and these several l i g a n d s i n p o l a r s o l v e n t s ; these c a t i o n s were metathesized w i t h NH4PF6 and i s o l a t e d as PF6 o f Ru(C5H5) ( PMe3)zC1 w i t h AgBF4 i n MeCN g i v e s [Ru(C5H5) ( PMe3),(MeCN)]BF4 and t h e r e a c t i o n w i t h NOPF6 g i v e s [Ru(C5H5) (PMe3)2(NO)](PF6)2. r e a c t i o n o f Ru(C5H5)(C0)2C1 w i t h PMe3 g i v e s predominately [Ru(C5H5)(CO)-A r e a c t i o n w i t h dpe occurs The compounds, -s a l t s . The r e a c t i o n The 205

Kinetics of phosphine substitution in CpRu(PPh3)2X (X = Cl, Br, I, N3, and NCO)

“…Chloroform-d 1 and benzene-d 6 (Cambridge Isotope Laboratories) were puried by distillation from CaH 2 and Na/benzophenone, respectively. Ruthenium(II) compounds CpRu(PPh 3 ) 2 Cl (1a), 11 CpRu(PPh 3 ) 2 Br (1b), 12 CpRu(PPh 3 ) 2 I (1c), 12 CpRu(PPh 3 ) 2 N 3 (1d), 13 CpRu(PPh 3 ) 2 NCO (1e), 12 CpRu(PPh 3 ) 2 H (1f), 12 CpRu(PPh 3 ) 2 F (1g), 14 CpRu(PPh 3 ) 2 SnF 3 (1h), 13 CpRu(PPh 3 ) 2 SnCl 3 (1i), 13 and CpRu(PPh 3 )(PPh 2 Me)Cl (2a), 15 were prepared by literature procedures. Melting points were determined in capillary tubes using an Electrothermal 9110 melting point apparatus and are uncorrected.…”

Optimised Syntheses of the Half-Sandwich Complexes FeCl(dppe)Cp*, FeCl(dppe)Cp, RuCl(dppe)Cp*, and RuCl(dppe)Cp

“…Workup consists of reduction of the solution volume and addition of hexanes to precipitate the product, which is recovered by a simple filtration. This procedure is essentially very similar to the wealth of previous reports, [42,43,45,46,66,[75][76][77][78][79][80] however taking care to employ the correct stoichiometric ratio of ruthenium to phosphine allows the product to be obtained in high yield and purity directly from the reaction mixture.…”

“…Three separate groups reported the synthesis of RuCl(dppe)Cp nearly simultaneously in late 1979 -early 1980, [42,75,76] by thermally driven phosphine exchange of 1,2-bis(diphenylphosphino)ethane with RuCl(PPh3)2Cp in refluxing benzene or toluene in yields of ca. 80%.…”

“…[42,81] In contrast, the greater stability of the five-membered chelate in RuCl(dppe)Cp leads to ready formation of this species from RuCl(PPh3)2Cp and 1,2-bis(diphenylphosphino)ethane under a range of concentrations. [42,43,45,46,66,[75][76][77][78][79][80] As described below, the 1:1 reaction of RuCl(PPh3)2Cp and 1,2bis(diphenylphosphino)ethane in refluxing toluene yields only the desired complex RuCl(dppe)Cp (94% isolated yield, 5.5 mmol scale) even from relatively concentrated solutions.…”

“…[85] However, the synthesis of this precursor [RuCp(C10H10)] + , among other difficulties, requires ruthenocene (involving a challenging synthesis itself) [86] as a starting material and includes a 50 hour reflux. [87] The most regularly used route to RuCl(dppe)Cp, based on the procedures for ligand exchange from RuCl(PPh3)2Cp developed by Bruce, [42] Davies [75] and Treichel, [76] is recognisably robust. However, we felt there may be a possibility of intended to mimic that used in the synthesis of RuCl(PPh3)2Cp [67] and RuCl(PPh3)2Cp*, [66] however the desired product was not obtained.…”