Investigations of Pyridine-2-thiol as a Ligand: Synthesis and X-ray Structures of the Mixed Mo−Mn Dinuclear Complex CpMoMn(CO)3(μ-CO)(μ-η2-pyS)(μ-η1-pyS), the Electron-Deficient Trimolybdenum Cluster Cp3Mo3(μ-CO)2(μ-S)(μ3-S)(μ-η2-NC5H4), and the Mononuclear CpMo(CO)2(μ-η2-pyS)

The reaction of Mn2(CO)6(pyS)2 (1) with (CpMo(CO)3)2 (2) at 110 °C gives the heterodinuclear complex CpMoMn(CO)3(μ-CO)(μ-η2-pyS))(μ-η1-pyS) (3), the mononuclear molybdenum
complex CpMo(CO)2(μ-η2-pyS) (4), and the 46-electron trimolybdenum cluster Cp3Mo3(μ-CO)2(μ-S)(μ3-S)(μ-η2-NC5H4) (5). Compound 4 could also be prepared in high yield from the
reaction of 2 with pyridine-2-thiol at 110 °C. Compound 3 represents a rare example of a
Mo−Mn heterodinuclear complex containing a μ-η2-pyridine-2-thiolato, a μ-η1-pyridine-2-thiolato, and a cyclopentadienyl ligand. The 46-electron compound 5 represents a unique
example of a trimolybdenum compound containing three cyclopentadienyl ligands, an ortho-metalated pyridyl ligand, a capping sulfido, a bridging sulfido, and two semibridging CO
ligands. Curiously, although this complex is formally electron deficient, it is unreactive toward
two-electron donors. The structures of all the compounds have been unambiguously
established by single-crystal X-ray crystallography.

在110°C下，Mn2(CO)6(pyS)2 (1)与(CpMo(CO)3)2 (2)的反应生成异核配位复合物CpMoMn(CO)3(μ-CO)(μ-η2-pyS))(μ-η1-pyS) (3)，单核钼复合物CpMo(CO)2(μ-η2-pyS) (4)，以及46电子的三钼簇Cp3Mo3(μ-CO)2(μ-S)(μ3-S)(μ-η2-NC5H4) (5)。化合物4还可通过2与吡啶-2-硫醇在110°C的反应以高收率制备。化合物3代表了一种罕见的含有μ-η2-吡啶-2-硫醇配体、μ-η1-吡啶-2-硫醇配体和环戊二烯配体的Mo-Mn异核复合物的实例。46电子的化合物5代表了一种独特的含有三个环戊二烯配体、邻金属化吡啶配体、封端硫醇、桥连硫醇和两个半桥连CO配体的三钼化合物的例子。令人好奇的是，尽管该复合物在形式上电子不足，但它对二电子供体不活泼。所有化合物的结构均通过单晶X射线晶体学得到了明确的确定。