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由于闭式碳硼烷(CB11H12-和C2B10H12)丰富的化学,它们已引了人们很多的关注.半夹芯16e化合物Cp#M(E2C2B10H10)(Cp#=η5-C5H5,η5-C5Me5;M=Co,Rh,Ir;E=S,Se)和半夹芯16e化合物(p-cymene)M(E2C2B10H10)(M=Ru,Os;E=S,Se)具有相似的结构特点,即含有一个二硫(硒)代闭式碳硼烷配体.由于分子结构中都存在不饱和的16e金属中心、两个配位多样的S(Se)原子及B-H键可活化的碳硼烷笼子,这些半夹芯式有机金属16e化合物已展现了丰富多样的反应性.由此,人们合成了一系列结构新颖的有机金属碳硼烷化合物.目前,KangSO课题组,HerberholdM课题组及燕红课题组已广泛研究并报道了半夹芯式含[E2C2B10H10]2-(E=S,Se)配体的有机金属16e化合物与炔烃配体R1C≡CR2(R1=H,CO2Me;R2=Ph,Fc,CO2Me,etc.)的反应性.本文报道了半夹心16e化合物,Cp*Co(S2C2B10H10)(1)(Cp*=pentamethylcyclopentadienyl),与炔酮HC≡C-C(O)R(R=OMe,Me,Ph)的反应性.(1)Cp*Co(S2C2B10H10)与过量的丙炔酸甲酯(HC≡C-CO2Me)反应产生了五个18e化合物2～6.其中,2是在碳硼烷B(3)/B(6)位点发生取代反应的产物,其分子结构含有B-CH2结构单元.有趣的是,化合物3～6则是通过两分子的炔烃在一个Co-S键上分别以头尾、头头、尾尾及尾头方式发生双分子加成的产物,为四个几何同分异构体,且它们首次从此类反应体系中同时分离得到.(2)Cp*Co(S2C2B10H10)与过量的3-丁炔-2-酮(HC≡C-C(O)Me)反应产生了化合物7和8.这两个半夹心式18e化合物是通过两分子的炔烃在一个Co-S键上分别以头尾和头头方式发生双分子加成的产物.(3)Cp*Co(S2C2B10H10)与过量的苯基乙炔基酮(HC≡C-C(O)Ph)反应产生了化合物9和10.化合物9和10的分子结构与化合物7和8类似,即含有一个六圆环结构单元(Co-C=C-C=C-S).化合物3,7,9及4,8,10代表了两类更稳定构像.因此,在上述反应中,半夹芯式16e化合物Cp*Co(S2C2B10H10)展现出了其独特的反应性,这也有利于我们理解结构单元Cp*Co和CpCo之间的差别对这类半夹芯式16e化合物反应性的影响.
They have attracted much attention due to the rich chemistry of the closed carborane (CB11H12- and C2B10H12). The semi-sandwich 16e compound Cp # M (E2C2B10H10) (Cp # = η5-C5H5, η5-C5Me5; M = (M = Ru, Os; E = S, Se) has the similar structural characteristics as the p-cymene M (E2C2B10H10) Sulfur (selenium) -based carborane ligands.The unsaturated 16e metal centers, two coordinated S (Se) atoms and BH bond-activated carborane cages exist in the molecular structure, A series of novel organometallic carborane compounds have been synthesized by sandwich-type organometallic 16e compounds.At present, the KangSO, Herberhold and Yanhong groups have been widely used It has been reported and reported that the semi-sandwich organometallic 16e compound containing [E2C2B10H10] 2- (E = S, Se) ligand and the alkyne ligand R1C≡CR2 (R1 = H, CO2Me; R2 = Ph, Fc, , etc.) In this paper, we report the synthesis of half-sandwich 16e compounds with Cp * = (pentamethylcyclopentadienyl) (Cp * = pentamethylcyclopentadienyl) ) Reactivity of (1) Cp * Co (S2C2B10H10) with excess The reaction of methyl alkynoate (HC≡C-CO2Me) yields five 18e compounds 2 to 6. Among them, 2 is the product of the substitution reaction at the carborane B (3) / B (6) Contains B-CH2 structural units Interestingly, compounds 3-6 are the products of bimolecular addition via two molecular alkynes on the Co-S bond at the head, tail, head, tail and tail, respectively (2) Cp * Co (S2C2B10H10) and excess 3-butyn-2-one (HC≡CC (O) Me) to give compounds 7 and 8. These two half-sandwich 18e compounds are the products of bimolecular addition in the head-end and head-end, respectively, on one Co-S bond by two molecules of alkyne. (3) Reaction of Cp * Co (S2C2B10H10) with an excess of phenylethynyl ketone (HC≡CC (O) Ph) yielded compounds 9 and 10. The molecular structures of compounds 9 and 10 are similar to compounds 7 and 8, ie contain one six circle Ring structure units (Co-C = CC = CS) .Compounds 3,7,9 and 4,8,10 represent two more stable conformations Thus, in the above reaction, the semi-sandwich 16e compound Cp * Co (S2C2B10H10) showed its unique response , Which will also help our understanding of the influence of the difference between the structural unit and Cp * Co CpCo half of such sandwich-type reactive compound 16e.