A. V. Rooy, P. Kamer, P. V. Leeuwen
May 15, 1997
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Influential Citations
13
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Journal
Journal of Organometallic Chemistry
Abstract
Abstract The stoichiometric hydroformylation reaction of allyldiphenylphosphine with RhH(CO) 2 ( 2 ) ( 2 is a bulky diphosphite) was studied using 1 H and 31 P NMR spectroscopy. Reaction of equimolar amounts in benzene resulted in the formation of RhH(CO)(CH 2 =CHCH 2 PPh 2 )( 2 ) in which all three phosphorus ligands are coordinated equatorially ( 4 ). When 4 was heated, hydride migration occurred leading to two products. Migration to the terminal carbon gave 5 , Rh(CO)(PPh 2 CH 2 CH 2 CH 2 )( 2 ). Migration of the hydride to the internal carbon atom was rapidly followed by CO insertion, resulting in the acyl compound 6 , containing a five-membered rhodacycle. Complex 6 did not undergo reaction with H 2 . Reaction of 5 with CO reversibly yielded acyl complex 7 , containing a six-membered rhodacycle. Hydrogenation of 5 yielded 8 , the diphenylpropylphosphine analogue of 4 .