Isomerization of RuCl2(Cyttp) (Cyttp=C6H5P(CH2CH2CH2P(C6H11)2)2) in solution

Synthesis and Characterization of Ruthenium(II) Complexes Containing Chiral Bis(ferrocenyl)−P3or −P2S Ligands. Asymmetric Transfer Hydrogenation of Acetophenone

“…In the temperature range from 243 to 193 K, however, the slow-motion regime is attained by all compounds to give resolved patterns with J PP values ranging from 27 to 38 Hz. A fac arrangement of all ligands about the metal center can thus be anticipated. , Stereochemical nonrigidity in solution is a typical characteristic of many five-coordinate ruthenium(II) complexes with linear tridentate phosphine ligands 3complex(Cy)P(Ph)P A (Ph)P B [( S )-( R )-Pigiphos]RuCl 2 ( 14 )294 K81.02 (bs)64.66 (bs)19.12 (bs) 243 K79.55 (dd)69.71 (t); J PP = 35.714.52 (t); J PP = 32.1 [( R )-( S )-8-Me-Pigiphos]RuCl 2 ( 15 ) c 71.92 (t); J PP = 38.666.09 (t)6.50 (t) [( R )-( S )-4-CF 3 -Pigiphos]RuCl 2 ( 16 ) d 81.15 (t)50.88 (t)34.18 (t); J PP = 36.0 [( S )-( R )-8-CF 3 -Pigiphos]RuCl 2 ( 17 )294 K102.21 (bs)70.46 (bs)53.4 (bs) 223 K87.87 (dd); J PP = 27.5, J PP = 36.352.75 (dd) (2P)[( S )-( R )-S-Pigiphos]RuCl 2 ( 18 )50.31 (d); J PP = 36.837.49 (d) { mer -[( S )-( R )-Pigiphos]Ru(CH 3 CN) 3 } 2+ ( 19 )77.0429.40; f J PP A = 23.5, J P A P B = 264.520.24; f J PP B = 29.8 {[( S )-( R )-Pigiphos]RuCl(CH 3 CN) 2 } + ( 20 ) b 85.19 (t); J PP = 29.835.42 (t)32.18 (t) { fac -[( S )-( R )-Pigiphos]Ru(CH 3 CN) 3 } 2+ ( 21 )81.50 (t); J PP = 30.540.55 (t)31.22 (t) {[( R )-( S )-8-Me-Pigiphos]Ru(CH 3 CN) 3 } 2+ ( 22 )83.71 (t); J PP = 30.645.47 (t)31.31 (t) {[( R )-( S )-4CF 3 -Pigiphos]Ru(CH 3 CN) 3 } 2+ ( 23 )81.92 (t); J PP = 33.352.01 (t)35.24 (t) {[( S )-( R )-8CF 3 -Pigiphos]RuCl(CH 3 CN) 2 } + ( 24 )86.59 (t); J PP = 31.051.67 (t)38.71 (t) {[( S )-( R )-S-Pigiphos]Ru(CH 3 CN) 3 } 2+ ( 25 ) e 52.62 (d); J PP = 30.243.56 (d) [( S )-( R )-Pigiphos]Ru(CF 3 CO 2 ) 2 ( 26 )THF- d 8 , 294 K102.26 (bs)47.32 (bs)44.56 (bs) THF- d 8 , 253 K101.30 (dd); J PP A = 30.5, J PP B = 45.7…”

“…In particular, from a comparison with the 31 P NMR spectra of the free ligands (Table ), one may distinguish the phosphorus atoms trans to chlorine from those with no trans ligand by the upfield shift of ca . 30 ppm of their resonance. 7d,− By using this simple criterion, the Pigiphos and 8-Me-Pigiphos complexes 14 and 15 can be assigned a fac square-pyramidal structure with an apical PhP group (Chart ), whereas the 4-CF 3 -Pigiphos and 8-CF 3 -Pigiphos complexes 16 and 17 are assigned a fac trigonal- bipyramidal structure with one chloride and one terminal phosphorus atom occupying the axial positions.

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Synthesis and Reactivity of Ru-, Os-, Rh-, and Ir-Halide−Sulfoxide Complexes

“…230 The mononuclear nature of fac-RuCl 2 (ttp), as opposed to the triply chloro-bridged bimetallic structure of [(etp)Ru-(µ-Cl) 3 Ru(etp)]Cl, was attributed to purely steric reasons, as the Ru(ttp) unit occupies a larger volume than Ru(etp). 230 Similar five-coordinate mononuclear complexes of formula RuCl 2 (P 3 ) were obtained from 8 with chiral bis(ferrocenyl)-triphosphine ligands such as (S)-(R)-Pigiphos (bis{(S)-1-(R)-2-(diphenylphosphino)ferrocenyl]ethyl}cyclohexylphosphine, Chart 18), 234 with the chiral ligand (R)-Ph 2 PCH 2 CH-(PPh 2 )CH 2 CH 2 PPh 2 (etp*), 235 with PhP(CH 2 CH 2 CH 2 P-(C 6 H 11 ) 2 ) 2 (Cyttp), 236 and with the tridentate phosphinite ligand MeC(CH 2 OPPh 2 ) 3 (triphox, Chart 18); 212 interestingly, this latter complex showed a triply chloro-bridged dimeric structure in the solid state, while in chloroform solution a significant part of the complex existed as the monomeric form.…”

Ruthenium(II) Complexes with Triphosphane Ligands Combining Planar, Phosphorus, and Carbon Chirality: Application to Asymmetric Reduction of Trifluoroacetophenone

“…Stereochemical nonrigidity, leading to the formation of isomers in solution, is typical for five-coordinate Ru II complexes with linear tridentate phosphane ligands. [7] Irrespective of the complex, the 31 P{ 1 H} NMR spectrum of each isomer consists of an AMQ pattern with 2 J P,P values ranging from 19.2 to 41 Hz, which anticipates The labeling scheme adopted is: P(1) ϭ CpPPh2, P(2) ϭ PPh, P(3) ϭ PPh 2 (see Figure 1). Table 1 for the labelling scheme).…”