TY - JOUR
T1 - Synthesis of heterometallic cluster compounds from Fe3(μ3-Te)2(CO)9 and comparisons with analogous sulfide clusters
AU - Bogan, Leonard E.
AU - Lesch, David A.
AU - Rauchfuss, Thomas B.
N1 - Funding Information:
This research was supported by the National Science Foundation (NSF CHE 81-06781). We also thank the Selenium-Tellurium Development Association and Engelhard Industries for loans of tellurium and platinum, respectively. T.B.R. is a recipient of a Camille and Henry Dreyfus Teacher-Scholar award.
PY - 1983/7/5
Y1 - 1983/7/5
N2 - Fe3Te2(CO)9 is shown to be a useful precursor to a variety of heterometallic carbonyl clusters in reactions which appear to proceed via the intermediacy of Fe2(Te2)(CO)6. Fe3Te2(CO)9 decomposed in polar solvents to give Fe2(Te2)(CO)6 which could be dimerized to Fe4Te4(CO)12. Fe3Te2(CO)9 reacted with C5H5Co(CO)2 and Pt(C2H4)(PPh3)2 to give good yields of (C5H5CO)Fe2Te2(CO)7 and Fe2PtTe2(CO)6(PPh3)2, respectively. (C5H5Co)Fe2Te2(CO)7 underwent reversible decarbonylation to give a mixture of two isomers of (C5H5Co)Fe2Te2(CO)6 as established by 125Te NMR spectroscopy. Upon reaction with Co2(CO)8, Fe3Te2(CO)9 gave Co2FeTe(CO)9 or Co4Te2(CO)11 depending on the reaction conditions. Co4Te2(CO)11, like Fe3Te2(CO)10 and (C5H5Co)Fe2Te2(CO)7, can be reversibly decarbonylated. The assembly of Co2FeTe(CO)9 may be mechanistically related to the conversion of Fe2(S2)(CO)6 to FeCo2S(CO)9 which was found to proceed via Co2Fe2S2(CO)11. Alternatively, Co2Fe2S2(CO)11 reacted photochemically with [C5H5Mo(CO)3]2 to give the known, chiral cluster (C5H5Mo)CoFeS(CO)8. While Fe2(Te2)(CO)6 thermally dimerized to Fe4Te4(CO)12, Fe2(S2)(CO)6 gave the analogous dimer only upon photolysis. In contrast to the stability of (C5H5CO)Fe2Te2(CO)7, the reaction of C5H5Co(CO)2 with Fe2(S2)(CO)6 gave only (C5H5CO)Fe2S2(CO)6 which is proposed to be structurally related to Fe3S2(CO)9 and not (C5H5Co)3S2 or Fe2PtS2(CO)6(PPh3)2.
AB - Fe3Te2(CO)9 is shown to be a useful precursor to a variety of heterometallic carbonyl clusters in reactions which appear to proceed via the intermediacy of Fe2(Te2)(CO)6. Fe3Te2(CO)9 decomposed in polar solvents to give Fe2(Te2)(CO)6 which could be dimerized to Fe4Te4(CO)12. Fe3Te2(CO)9 reacted with C5H5Co(CO)2 and Pt(C2H4)(PPh3)2 to give good yields of (C5H5CO)Fe2Te2(CO)7 and Fe2PtTe2(CO)6(PPh3)2, respectively. (C5H5Co)Fe2Te2(CO)7 underwent reversible decarbonylation to give a mixture of two isomers of (C5H5Co)Fe2Te2(CO)6 as established by 125Te NMR spectroscopy. Upon reaction with Co2(CO)8, Fe3Te2(CO)9 gave Co2FeTe(CO)9 or Co4Te2(CO)11 depending on the reaction conditions. Co4Te2(CO)11, like Fe3Te2(CO)10 and (C5H5Co)Fe2Te2(CO)7, can be reversibly decarbonylated. The assembly of Co2FeTe(CO)9 may be mechanistically related to the conversion of Fe2(S2)(CO)6 to FeCo2S(CO)9 which was found to proceed via Co2Fe2S2(CO)11. Alternatively, Co2Fe2S2(CO)11 reacted photochemically with [C5H5Mo(CO)3]2 to give the known, chiral cluster (C5H5Mo)CoFeS(CO)8. While Fe2(Te2)(CO)6 thermally dimerized to Fe4Te4(CO)12, Fe2(S2)(CO)6 gave the analogous dimer only upon photolysis. In contrast to the stability of (C5H5CO)Fe2Te2(CO)7, the reaction of C5H5Co(CO)2 with Fe2(S2)(CO)6 gave only (C5H5CO)Fe2S2(CO)6 which is proposed to be structurally related to Fe3S2(CO)9 and not (C5H5Co)3S2 or Fe2PtS2(CO)6(PPh3)2.
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U2 - 10.1016/0022-328X(83)85067-0
DO - 10.1016/0022-328X(83)85067-0
M3 - Article
AN - SCOPUS:0001129116
SN - 0022-328X
VL - 250
SP - 429
EP - 438
JO - Journal of Organometallic Chemistry
JF - Journal of Organometallic Chemistry
IS - 1
ER -