Preparation and reactions of tetrahedrane-type clusters containing a SCoFeM (M=Mo or W) core. The single crystal X-ray structure of the cluster (μ 3-S)CoFeMo(CO) 8[η 5-C 5H 4C(O)CH 2CH 2CO 2Me]

• Published in: Polyhedron 2001-06, Vol.20 (15), p.1859-1865
• Main Authors: Zhang, Yu-Hua, Yuan, Jian-Chao, Yin, Yuan-Qi, Zhou, Zhong-Yuan, Chan, Albert S.C.
• Format: Article
• Language: English
• Subjects: Chiral; Cluster complexes; Crystal structures; Diastereoisomers; Enantiomeric separation; Transition metals
• ISSN: 0277-5387
• DOI: 10.1016/S0277-5387(01)00778-1

Treatment of the monoanions {M(CO) 3[η 5-C 5H 4C(O)CH 2CH 2CO 2Me]} − with FeCo 2(CO) 9(μ 3-S) in refluxing THF gave the novel cluster complexes (μ 3-S)CoFeM(CO) 8[η 5-C 5H 4C(O)CH 2CH 2CO 2Me] (M=Mo, 1; M=W, 2). Reactions of the cluster (μ 3-S)CoFeMo(CO) 8[η 5-C 5H 4C(O)Me] ( 3) with amine derivatives 2,4-dinitrophenylhydrazine, thiosemicarbazide, (−)-5-(α-phenyl)semioxamazide and l-(+)-menthydrazide respectively at room temperature yielded four new hydrazone cluster complexes (μ 3-S)CoFeMo(CO) 8[η 5-C 5H 4C(NR)Me] [ 4– 7, R=NHC 6H 3-2,4-(NO 2) 2, NHC(S)NH 2, NHC(O)C(O)NHCH(Me)(C 6H 5) and NHCO 2(menthyl)]. However, cluster 1 only reacted with 2,4-dinitrophenylhydrazine to give the cluster (μ 3-S)CoFeMo(CO) 8[η 5-C 5H 4C(NR)Me] [ 8, R=NHC 6H 3-2,4-(NO 2) 2] under the same conditions. Although two kinds of optically active groups have been attached to the racemic cluster, the mixture of diastereoisomers produced cannot be separated chromatographically. The 13C NMR showed the presence of the diastereoisomers of clusters 5 and 6. Cluster 1 has been solved by single-crystal X-ray diffraction.