Cyclopentadienyl Rhenium Complexes

Diastereoselective Protonation, Substitution and Addition Reactions at Pseudotetrahedral Rhenium Complexes

“…The acetonitrile complex [CpRe(CO)(NO)(NCMe)]BF 4 ( 7 ) is a perfectly suited starting material for the synthesis of chiral half‐sandwich rhenium complexes 17–19. Fusing 7 together with a slight excess of racemic 3 under vacuum and without solvent gave a high yield of racemic 8 .…”

“…Borohydride reduction of the carbonyl ligand17 gave the methyl complexes 9 and ( R Re , S P / S Re , S P )‐ 9 , respectively (Scheme ). The success of the reaction is immediately evident from the disappearance of the CO stretching absorption in the infrared spectrum and new doublets in the 1 H and 13 C NMR spectra typical of a Re–CH 3 group.…”

“…X‐ray structures: Bruker SMART APEX CCD. The following starting materials were obtained as described in the literature: [CpRe(CO)(NO)(NCMe)]BF 4 ( 7 ),17 NaSH,43 PH(Me)(Ph),44 [( S C )‐ 4 ] 14. Acetylacetone and the thiols were converted into their sodium salts by adding a stoichiometric amount of sodium metal to solutions in ethanol, followed by evaporation to dryness.…”

Synthesis and Reactivity of 1,2‐ and 1,3‐Diphosphanes that Contain Four Chiral Rhenium Fragments: Architecturally Novel Tetrametallo‐DMPE and ‐DMPP Species that are Unprivileged Ligands for Enantioselective Catalysis

“…[(η 5 ‐C 5 H 5 )Re(NO)(PPh 3 ){CH 2 PH 2 CH 2 (CH 2 ) n CH 2 PH 2 CH 2 }(Ph 3 P)(ON)Re(η 5 ‐C 5 H 5 )] 2+ 2X – ( n /X = 0/PF 6 , 3; 0/BF 4 , 3'; 1/PF 6 , 4): ( A ) A Schlenk flask was charged with ( S )‐ 1 (0.327 g, 0.585 mmol)9,36,37 and CH 2 Cl 2 (15 mL), and was cooled to –60 °C. Then Ph 3 C + PF 6 – (0.250 g, 0.644 mmol) was added with stirring.…”

“…Other groups are also making important contributions to the design and application of non‐ferrocenyl metal‐containing ligands in catalysis 8. We have often but not exclusively4b used the easily resolved9 chiral rhenium fragment [(η 5 ‐C 5 H 5 )Re(NO)(PPh 3 )] + ( I ). Two types of bidentate ligands have been prepared, as illustrated by the diphosphanes II and diamine IIIa in Figure 1.…”