Adams Richard D, Miao Shaobin, Smith Mark D, Farach Horatio, Webster Charles Edwin, Manson Josiah, Hall Michael B
Department of Chemistry and Biochemistry, University of South Carolina, Columbia, South Carolina 29208, USA.
Inorg Chem. 2004 Apr 19;43(8):2515-25. doi: 10.1021/ic0354419.
The reaction of Mn(2)(CO)(7)(mu-S(2)) with CpNi(CO) yielded the paramagnetic new compound Cp(2)Ni(2)Mn(CO)(3)(mu(3)-S)(2) (1) and a new hexanuclear metal product Cp(2)Ni(2)Mn(4)(CO)(14)(mu(6)-S(2))(mu(3)-S)(2) (2). Structurally, compound 1 contains two triply bridging sulfido ligands on opposite sides of an open Ni(2)Mn triangular cluster. EPR and temperature-dependent magnetic susceptibility measurements of 1 show that it contains one unpaired electron. The electronic structure of 1 was determined by Fenske-Hall molecular orbital calculations which show that the unpaired electron occupies a low lying antibonding orbital delocalized unequally across the three metal atoms. The selenium homologue Cp(2)Ni(2)Mn(CO)(3)(mu(3)-Se)(2) (3) was obtained from the reaction of a mixture of Mn(2)(CO)(10) and CpNi(CO) with elemental selenium and Me(3)NO.2H(2)O. It also has one unpaired electron. Compound 1 reacted with elemental sulfur to yield the dinickeldimanganese compound, Cp(2)Ni(2)Mn(2)(CO)(6)(mu(4)-S(2))(mu(4)-S(5)), 4, which can also be made from the reaction of Mn(2)(CO)(7)(mu-S(2)) with CpNi(CO) and sulfur. Compound 4 was converted back to 1 by sulfur abstraction using PPh(3). The reaction of Mn(2)(CO)(10) with CpNi(CO) in the presence of thiirane yielded the ethanedithiolato compound CpNiMn(CO)(3)(mu-SCH(2)CH(2)S) (5), which was also obtained from the reaction of Mn(4)(CO)(15)(mu(3)-S(2))(mu(4)-S(2)) with CpNi(CO) in the presence of thiirane. Compound 5 reacted with additional quantities of thiirane to yield the new compound CpNiMn(CO)(3)[mu-S(CH(2)CH(2)S)(2)], 6, which contains a 3-thiapentanedithiolato ligand that bridges the two metal atoms. Compound 6 was also obtained from the reaction of Mn(2)(CO)(10) with CpNi(CO) and thiirane. The molecular structures of the new compounds 1-6 were established by single-crystal X-ray diffraction analyses.
Mn(2)(CO)(7)(μ - S(2))与CpNi(CO)反应生成了顺磁性新化合物Cp(2)Ni(2)Mn(CO)(3)(μ(3)-S)(2) (1)和一种新的六核金属产物Cp(2)Ni(2)Mn(4)(CO)(14)(μ(6)-S(2))(μ(3)-S)(2) (2)。在结构上，化合物1在一个开放的Ni(2)Mn三角簇的相对两侧包含两个三桥连硫配体。对1进行的电子顺磁共振（EPR）和温度依赖的磁化率测量表明它含有一个未成对电子。通过Fenske - Hall分子轨道计算确定了1的电子结构，结果表明未成对电子占据一个低能量反键轨道，该轨道在三个金属原子间不均匀离域。硒同系物Cp(2)Ni(2)Mn(CO)(3)(μ(3)-Se)(2) (3)是由Mn(2)(CO)(10)和CpNi(CO)的混合物与元素硒及Me(3)NO·2H(2)O反应得到的。它也有一个未成对电子。化合物1与元素硫反应生成二镍二锰化合物Cp(2)Ni(2)Mn(2)(CO)(6)(μ(4)-S(2))(μ(4)-S(5))，即4，它也可由Mn(2)(CO)(7)(μ - S(2))与CpNi(CO)及硫反应制得。化合物4通过使用三苯基膦（PPh(3)）夺取硫又转化回1。在硫杂环丙烷存在下，Mn(2)(CO)(10)与CpNi(CO)反应生成乙二硫醇盐化合物CpNiMn(CO)(3)(μ - SCH(2)CH(2)S) (5)，它也可由Mn(4)(CO)(15)(μ(3)-S(2))(μ(4)-S(2))与CpNi(CO)在硫杂环丙烷存在下反应得到。化合物5与额外量的硫杂环丙烷反应生成新化合物CpNiMn(CO)(3)[μ - S(CH(2)CH(2)S)(2)]，即6，它含有一个桥连两个金属原子的3 -硫杂戊二硫醇盐配体。化合物6也可由Mn(2)(CO)(10)与CpNi(CO)及硫杂环丙烷反应得到。通过单晶X射线衍射分析确定了新化合物1 - 6的分子结构。
