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Substitution and Catalytic Chemistry of Gyroscope‐Like Complexes Derived from Cl–Rh–CO Rotators and Triply trans Spanning Di(trialkylphosphine) Ligands
Author(s) -
Estrada Alexander L.,
Jia Tiezheng,
Bhuvanesh Nattamai,
Blümel Janet,
Gladysz John A.
Publication year - 2015
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.201500953
Subject(s) - chemistry , hydroformylation , rhodium , catalysis , medicinal chemistry , carbonylation , substitution reaction , denticity , stereochemistry , bromide , crystal structure , crystallography , carbon monoxide , inorganic chemistry , organic chemistry
Reactions of trans ‐[Rh(CO)(Cl){P{(CH 2 ) 14 } 3 P 2 (Rh–P 2 ) }] ( 1 ) with ZnPh 2 , MeLi, or NaBH 4 give the chloride‐substitution products trans ‐[Rh(CO)(Ph){P{(CH 2 ) 14 } 3 P 2 (Rh–P 2 ) }] ( 3 , 89 %), trans ‐[Rh(CO)(Me){P{(CH 2 ) 14 } 3 P 2 (Rh–P 2 ) }] (94 %, 92 % purity), and trans ‐[Rh(CO)(H 2 BH 2 ){P{(CH 2 ) 14 } 3 P 2 (Rh–P 2 ) }] ( 5 , 99 %). The crystal structures of 3 , 5 , and the corresponding (fortuitously obtained) bromide complex are determined, and the ability of the X–Rh–CO moieties to rotate is interpreted in terms of their effective radii and the void space within the dibridgehead diphosphine cage. Reaction of 1 and excess PMe 3 gives the diphosphine substitution product trans ‐[Rh(CO)(Cl)(PMe 3 ) 2 ] (89 %) and the dibridgehead diphosphine P[(CH 2 ) 14 ] 3 P (58 %). Complex 5 serves as a catalyst precursor for the hydroformylation of 1‐octene (neat or THF, 60 °C, 75 psig 1:1 CO/H 2 ). The locus of catalysis with respect to the diphosphine cage is discussed.