新型双四面体过渡金属簇合物的合成与表征

利用Co₂(CO)₈与Cl₃CC(O)OCH₂]₂的反应合成了以C(O)OCH₂CH₂OC(O)桥联两个Co₃C四面体骨架为特征的新型双四面体簇合物(CO)₉Co₃(μ₃-C)C(O)OCH₂]₂(1);1与不同物质的量比的NaM(CO)₃C₅H₄R](M=Mo,W;R=H,C(O)Me)反应,得到一步交换的产物(CO)₉Co₃(μ₃-C)C(O)OCH₂CH₂OC(O)(μ₃-C)Co₂M(CO)₈(C₅H₄R)M=Mo,R=H(2);M=Mo,R=C(O)Me(3);M=W,R=H(4);M=W,R=C(O)Me(5)]或两步交换的产物(C₅H₄R)(CO)₈Co₂M(μ₃-C)C(O)OCH₂]₂M=Mo,R=H(6);M=Mo,R=C(O)Me(7);M=W,R=H(8);M=W,R=C(O)Me(9)].5或9分别与NaMo(CO)₃C₅H₅]以12的物质的量比反应得到含一个手性四面体骨架(CoMoWC)的(C₅H₅)(CO)₈Co₂Mo(μ₃-C)C(O)OCH₂CH₂O·C(O)(μ₃-C)CoMoW(CO)₇(C₅H₄C(O)Me)(C₅H₅)(10)或含两个手性四面体骨架(CoMoWC)的(C₅H₅)(C₅H₄C(O)Me)(CO)₇CoMoW(μ₃-C)C(O)OCH₂]₂(11);对化合物1_11进行了CH元素分析、IR和¹HNMR等表征.结果表明,在金属交换反应中处于不同簇环境下的Co(CO)₃基团反应活性不同.对化合物1进行了晶体X射线衍射分析.化合物1的晶体属单斜晶系,P2₁/n(#14)空间群,晶胞参数a=0.933 0(2)nm,b=1.519 7(4)nm,c=1.178 3(4)nm,=91.16(2)°,Z=2,F(000)=972.分子结构呈中心对称.

Synthesis and Characterization of Novel Double Tetrahedral Transition Metal Clusters

The reaction of Co₂(CO)₈ and C₁₃CC(O)OCH₂]₂ gave a novel double tetrahedral cluster compound((CO)₉Co₃(μ₃-C)C(O)OCH₂]₂ 1)containing two tetrahedral skeletons(Co₃C) linked by a C(O)OCH₂CH₂OC(O) bridge. The reaction of 1 with different molecular ratios of NaM(CO)₃C₅H₄R]M=Mo, W; R=H, C(O)Me] gave the one-step exchange products (CO)₉Co₃(μ₃-C)C(O)OCH₂CH₂OC(O)(μ₃-C)Co₂M(CO)₈(C₅H₄R)M=Mo, R=H(2); M=Mo, R=C(O)Me (3); M=W, R=H (4); M=W, R=C(O)Me (5)] or the two-step exchange products or the two-step exchange products (C₅H₄R)(CO)₈Co₂M(μ₃-C)C(O)OCH₂]₂M=Mo, R=H(6); M=Mo, R=C(O)Me (7); M=W, R=H (8); M=W, R=C(O)Me (9)]. By treating. By treating₅ or 9 with NaMo(CO)₃C₅H₅] in 1/2 molecular ratio, the compound (C₅H₅)(CO)₈Co₂Mo(μ₃-C)·C(O)OCH₂CH₂OC(O)(μ₃-C)CoMoW(CO)₇(C₅H₄C(O)Me)(C₅H₅)(10) or (C₅H₅)(C₅H₄·C(O)Me)(CO)₇CoMoW(μ₃-C)C(O)OCH₂]₂ (11) which has one or two chiral tetrahedral skeletons(CoMoWC)was obtained. Compounds 1_11 were characterized by C/Hanalyses, IRand ¹HNMR. The results indicate that the Co(CO)₃1/n (#14) and lattice parameters, a=0.9330(2) nm, b=1.5197(4) nm, c=1.1783(4) nm, β=91.16(2)°, Z=2, F (000)=972.