Synthesis of triphenyl‐phosphine, ‐arsine and ‐stibine derivatives of phenylmethinyltricobalt enneacarbonyls and their catalytic properties

Mono‐substituted triphenyl‐phosphine, ‐arsine and ‐stibine derivatives of phenylmethinyltricobalt enneacarbonyls PhCCo 3 (CO) 8 L (where L PPh 3 , AsPh 3 and SbPh 3 ) were synthesized. The Co(2 p 3/2 ) binding energy ( E b ) was lowered from 781.3 eV in PhCCo 3 (CO) 9 , to 780.0 eV in PhCCo 3 (CO) 8 PPh 3 , to 780.3 eV in PhCCo 3 (CO) 8 AsPh 3 and to 780.5 eV in PhCCO 3 (CO) 8 SbPh 3 . Hydroformylation selectivity to total aldehyde and alcohol of the substituted clusters PhCCo 3 (CO) 8 L was about 100%, but that of the parent cluster PhCCo 3 (CO) 9 was 93.8%. Hydroformylation products of styrene and di‐isobutene were the completely normal aldehyde when using PhCCo 3 (CO) 8 AsPh 3 as catalyst.