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|標題:||The reactions of 4,6-dimethyl-2-mercaptopyrimidine with dimetallic compounds: diiron nonacarbonyl and cyclopentadienylmolybedenum tricarbonyl dimer||作者:||Hong, F.E.
|關鍵字:||mercaptopyrimidine;dimetallic compound;isomeric forms;mu(4)-S;centered spirocyclic form;metal-promoted reaction;crystal-structure;cluster complexes;= s;<(mu-rs)(mu-s)(fe-2(co)(6))(2)(mu(4)-s)>(-);reactivity;ligands;anions||Project:||Journal of Organometallic Chemistry||期刊/報告no：:||Journal of Organometallic Chemistry, Volume 655, Issue 1-2, Page(s) 49-54.||摘要:||
Treatment of 4,6-dimethyl-2-mercaptopyrimidine with diiron nonacarbonyl at 25 degreesC in THF, gave two isomeric compounds, [(eta(2)-mu(1)-C,N-C6H7N2)Fe-2(CO)(6)(mu(4)-S)Fe-2(CO)(6)(mu(2)-S-SC6H7N2)] (2) and (3). The X-ray structure analysis revealed that the cores of 2 and 3 are (mu(4)-S)Fe-4 units with centered spirocyclic forms. On one side of the molecule, one diiron fragment is bridged by a pyrimidyl ligand through its nitrogen and carbon atoms; on the other side, the other diiron fragment is doubly bridged by a pyrimidinethiolate through its sulfur atom. Inter-conversion between 2 and 3 occurred rather slowly at 25 degreesC in solution; nevertheless, the rate was enhanced in the presence of high pressure of carbon monoxide. A major product, [(eta(2)-mu(1)-C,N-C6H7N2)Fe-2(CO)(6)(mu(4)-S)Fe-2(CO)(5)(P(OMe)(3))(mu-S-SC6H7N2)] (4), was obtained while 2 was treated with P(OMe)(3) in THF at 25 degreesC for 24 h. In contrast, the reaction of 4,6-dimethyl-2-mercaptopyrimidine with cyclopentadienylmolybedenum tricarbonyl dimer in THF at 50 degreesC, gave an unimetallic complex, [(eta(5)-C5H5)Mo(CO)(2)(eta(2)-S,N-SC6H7N2)] (5). Crystal structure of 5 revealed that the deprotonated mercaptopyrimidine acted as a bidentate ligand. (C) 2002 Elsevier Science B.V. All rights reserved.
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