10.1021/om0204686.s001
Detlef Selent
Detlef
Selent
Wolfgang Baumann
Wolfgang
Baumann
Rhett Kempe
Rhett
Kempe
Anke Spannenberg
Anke
Spannenberg
Dirk Röttger
Dirk
Röttger
Klaus-Diether Wiese
Klaus-Diether
Wiese
Armin Börner
Armin
Börner
Reactions of a Hydroxy Phosphonite Ligand in the
Coordination Sphere of Rhodium(I)
American Chemical Society
2003
phenoxy phosphonite chelate
hydroxy phosphonite
transformation
cleavage
bond
rhodium
bidentate phosphorus ligand
phosphite
hydroformylation
CO
hydroxy phosphonite ligand
Hydroxy Phosphonite Ligand
2003-10-13 00:00:00
Dataset
https://acs.figshare.com/articles/dataset/Reactions_of_a_Hydroxy_Phosphonite_Ligand_in_the_Coordination_Sphere_of_Rhodium_I_/3361495
The complexation behavior of 6-(3,3‘-di-<i>tert</i>-butyl-5,5‘-dimethoxy-2-hydroxy-2‘-oxybiphenyl)-6<i>H</i>-[<i>c</i>,<i>e</i>]-1,2-oxaphosphorine, which generates an active and <i>n</i>-regioselective rhodium(I)
catalyst for the isomerizing hydroformylation of internal octenes, was studied. Investigations
in the absence of CO/H<sub>2</sub> revealed that coordination of the phenolate moiety of the hydroxy
phosphonite on the rhodium center is possible. Interestingly, under conditions related to
the hydroformylation (syngas, higher temperature and P:Rh ratios) the ligand suffers two
transformations. The first is based on a transesterification reaction involving 2 equiv of the
hydroxy phosphonite, giving rise to a substituted biphenol and a symmetric bidentate
phosphorus ligand of a heretofore uncertain structure. The second transformation is
concerned with a selective Rh(I)-catalyzed P−C bond cleavage of the initial phosphonite
structure under the formation of a phosphite. X-ray structural analyses will illustrate the
structures of rhodium(I) complexes bearing the original hydroxy phosphonite ligand, a
phenoxy phosphonite chelate, and a phosphite formed by selective P−C bond cleavage,
respectively.