CUBIC GROUP-13 HETEROSILOXANES WITH 4 CO-3(CO)(9)C CLUSTER UNITS AS SUBSTITUENTS - NOVEL SOLUBLE MODEL COMPOUNDS FOR SYNTHETIC ZEOLITES SHOWING CATALYTIC ACTIVITY IN HYDROFORMYLATION REACTIONS

The reactions between the cobalt carbonyl anchored silanetriol Co-3(CO )(9)CSi(OH)(3) (1) and EMe(3) (E = Al, Ga and In) in THF result in the formation of the respective group 13 heterosiloxanes [Co-3(CO)(9)CSiO (3)E . THF](4) (Al (2); Ga (3); In (4)) in good yields. The new hetero siloxanes have been extensively characterized by means of their analyt ical and spectroscopic (mass, IR, and NMR) data. Additionally, the mol ecular structure of the Al complex 2 has been determined by X-ray diff raction studies. The compound contains a cubic Al4O12Si4 core with fou r Co-3-(CO)(9)C cluster units anchored on each of the silicon atoms at the alternating corners of the cube. Interestingly, there are three d ifferent types of Co-3(CO)(9)C cluster units within the same molecule based on the mode of coordination of the CO ligands. In order to test the utility of these compounds in catalytic conversions, hydroformylat ion reactions involving l-hexene as substrate have been carried out at 120 degrees C under a H-2/CO initial pressure of 70 bar. A series of solution studies of the catalytic mixture (such as time-dependent IR, NMR, and MS) have been carried out in order to identify the catalytic active species in the process. The Al- and Ga-containing heterosiloxan es show a better hydroformylation activity compared to the In analogue . The regioselectivity of the hydroformylation reactions with 2 is fou nd to be over 60%. The hydroformylation presumably proceeds via the de composition of Co-3(CO)(9)C cluster fragments into Co-2(CO)(8) units i n the case of catalysts 2 and 3.