OCTAHEDRAL METAL CARBONYLS .11. REACTIONS OF GROUP VIB METAL CARBONYL DERIVATIVES OF 2,2,7,7-TETRAMETHYL-3,6-DITHIAOCTANE

Cr(CO)6, Mo(CO)6, and W(CO)6 react with 2,2,7,7-tetramethyl-3,6-dithiaoctane (DTO) to give (DTO)M(CO)4 complexes. The bidentate ligand is readily replaced in these complexes by phosphites (L) to give L2M(CO)4 products. Kinetic data for all three metals indicate that the replacement occurs through a mechanism involving initial reversible dissociation of one end of the DTO ligand. DTO is also replaced by norbornadiene to give (C7H8)W(CO)4, thus suggesting the potential usefulness of (DTO)M(CO)4 complexes as synthetic intermediates in the preparation of organometallic complexes of the group VIb metals. © 1969, American Chemical Society. All rights reserved.