Syntheses of double- and triple-decker clusters of osmium and cobalt metals linked by cyclotetradeca-1,8-diyne ligands

Abstract

Photoirradiation of Os 3(CO) 10(C 14H 20) ( 1) in n-hexane produces the double-decker cluster [Os 3(CO) 9(C 28H 40)] [Os 3(CO) 10] ( 7), which can also be prepared from the reaction of Os 3(CO) 9(C 28H 40) ( 2) and Os 3(CO) 10(NCMe) 2. Further reaction of 7 with Os 3(CO) 10(NCMe) 2 affords the triple-decker cluster [Os 3(CO) 9(C 28H 40)][Os 3(CO) 10] 2 ( 8). The bis(diyne) complex Os 3(CO) 8(C 14H 20) 2 ( 3) reacts with Os 3(CO) 10(NCMe) 2 sequentially to yield the double-decker cluster [Os 3(CO) 8(C 14H 20) 2][Os 3(CO) 10] ( 4) and the triple-decker cluster [Os 3(CO) 8(C 14H 20) 2][Os 3(CO) 10] 2 ( 5). Treatment of 3 with Co 2(CO) 8 at room temperature leads to the mixed-metal triple-decker cluster [Os 3(CO) 8(C 14H 20) 2][Co 2(CO) 6] 2 ( 6), while the reaction of 2 and Co 2(CO) 8 produces [Os 3(CO) 9(C 28H 40)][Co 2(CO) 6] 2 ( 9) and [Os 2(CO) 6(C 28H 40)][Co 2(CO) 6] 2 ( 10). Compound 10, which involves cluster degradation from Os 3 to Os 2, has been structurally characterized by an X-ray diffraction study.