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- W1963554048 abstract "The P–Ph cleavage of phenyldibenzophosphole ( 1 ) with lithium in THF gives lithium dibenzophospholide ( 2 ). Reaction of 2 with ethyleneglycol ditosylate produces the known chelate ligand 1,2-bis(dibenzophospholyl)ethane ( 3 ) in good yield. Similarly, 2 and (2 R ,3 R )-butanediol ditosylate give the new chiral chelate ligand (2 S ,3 S )-bis(dibenzophospholyl)butane ( 4 ). Ligand exchange of [CpRu(PPh 3 ) 2 Cl] with 3 or 4 yields the halfsandwich complexes [CpRu(C 12 H 8 PC 2 H 4 PC 12 H 8 )Cl] ( 5 ) and [CpRu(( S , S )-C 12 H 8 PCHMeCHMePC 12 H 8 )Cl] ( 6 ). Complex 6 was characterized crystallographically (monoclinic, space group P 2 1 (no. 4), a =820.6(4), b =1501.0(3), c =1172.8(6) pm, β =108.87(2)°, V =1.367(1)×10 9 pm 3 , Z =2). The most conspicuous feature of the structure of 6 is the perfect coplanarity of the two dibenzophosphole moieties imposed by their steric interaction with the Cp ligand. Complex 6 and the thiophene complex [CpRu(( S , S )-C 12 H 8 PCHMeCHMePC 12 H 8 )(SC 4 H 4 )]BF 4 ( 7 ) derived therefrom are remarkably unreactive with regard to ligand substitutions. A possible explanation is the lack of intramolecular M⋯H–C stabilization en route to the transition state of ligand substitution. The enantiomeric purity of 6 and 7 could nevertheless be demonstrated by conversion to diastereomerically pure [CpRu(( S , S )-C 12 H 8 PCHMeCHMePC 12 H 8 )(( S )-CNCHMePh)]BF 4 ( 8 )." @default.
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- W1963554048 date "1998-06-01" @default.
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- W1963554048 title "Enantioselective organic syntheses using chiral transition metal complexes V. (2S,3S)-Bis(dibenzophospholyl)butane, a rigid (S,S)-CHIRAPHOS analog" @default.
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- W1963554048 doi "https://doi.org/10.1016/s0022-328x(98)00461-6" @default.
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