Carbon−Phosphorus Bond Activation of Tri(2-thienyl)phosphine at Dirhenium and Dimanganese Centers

Reaction of [Re2(CO)9(NCMe)] with tri(2-thienyl)phosphine (PTh3) in refluxing cyclohexane affords three substituted dirhenium complexes: [Re2(CO)9(PTh3)] (1), [Re2(CO)8(NCMe)(PTh3)] (2), and [Re2(CO)8(PTh3)2] (3). Complex 2 was also obtained from the room-temperature reaction of [Re2(CO)8(NCMe)2] with PTh3 and is an unusual example in which the acetonitrile and phosphine ligands are coordinated to the same rhenium atom. Thermolysis of 1 and 3 in refluxing xylene affords [Re2(CO)8(μ-PTh2)(μ-η1:κ1-C4H3S)] (4) and [Re2(CO)7(PTh3)(μ-PTh2)(μ-H)] (5), respectively, both resulting from carbon−phosphorus bond cleavage of a coordinated PTh3 ligand. Reaction of [Re2(CO)10] and PTh3 in refluxing xylene gives a complex mixture of products. These products include 3−5, two further binuclear products, [Re2(CO)7(PTh3)(μ-PTh2)(μ-η1:κ1-C4H3S)] (6) and [Re2(CO)7(μ-κ1:κ2-Th2PC4H2SPTh)(μ-η1:κ1-C4H3S)] (7), and the mononuclear hydrides [ReH(CO)4(PTh3)] (8) and trans-[ReH(CO)3(PTh3)2] (9). Binuclear 6 is structurally similar to 4 and can be obtained from reaction of the latter with 1 equiv of PTh3. Formation of 7 involves a series of rearrangements resulting in the formation of a unique new diphosphine ligand, Th2PC4H2SPTh. Reaction of [Mn2(CO)10] with PTh3 in refluxing toluene affords the phosphine-substituted product [Mn2(CO)9(PTh3)] (10) and two carbon−phosphorus bond cleavage products, [Mn2(CO)6(μ-PTh2)(μ-η1:η5-C4H3S)] (11) and [Mn2(CO)5(PTh3)(μ-PTh2)(μ-η1:η5-C4H3S)] (12). Both 11 and 12 contain a bridging thienyl ligand that is bonded to one manganese atom in a η5-fashion. The molecular structures of eight of these new complexes were established by single-crystal X-ray diffraction studies, allowing a detailed analysis of the disposition of the coordinated ligands.

在回流己烷中，[Re2(CO)9(NCMe)] 与三(2-噻基)磷烷 (PTh3) 反应，得到三种取代的二铑络合物：[Re2(CO)9(PTh3)] (1)、[Re2(CO)8(NCMe)(PTh3)] (2) 和 [Re2(CO)8(PTh3)2] (3)。复合物 2 还可以通过室温下 [Re2(CO)8(NCMe)2] 与 PTh3 的反应获得，这是一个不寻常的例子，其中乙腈和膦配体均与同一铑原子配位。在回流二甲苯中热解 1 和 3 可分别得到 [Re2(CO)8(μ-PTh2)(μ-η1:κ1-C4H3S)] (4) 和 [Re2(CO)7(PTh3)(μ-PTh2)(μ-H)] (5)，这两者均源于配位 PTh3 配体的碳-磷键断裂。在回流二甲苯中 [Re2(CO)10] 与 PTh3 的反应产生了一系列复杂的产物，包括 3-5、两种进一步的二核产物 [Re2(CO)7(PTh3)(μ-PTh2)(μ-η1:κ1-C4H3S)] (6) 和 [Re2(CO)7(μ-κ1:κ2-Th2PC4H2SPTh)(μ-η1:κ1-C4H3S)] (7)，以及单核氢化物 [ReH(CO)4(PTh3)] (8) 和反式-[ReH(CO)3(PTh3)2] (9)。二核 6 的结构类似于 4，可以通过与 1 当量的 PTh3 反应获得。7 的形成涉及一系列重排，最终形成一种独特的新的二膦配体 Th2PC4H2SPTh。在回流甲苯中，[Mn2(CO)10] 与 PTh3 的反应得到膦取代产物 [Mn2(CO)9(PTh3)] (10) 和两种碳-磷键断裂产物，[Mn2(CO)6(μ-PTh2)(μ-η1:η5-C4H3S)] (11) 和 [Mn2(CO)5(PTh3)(μ-PTh2)(μ-η1:η5-C4H3S)] (12)。11 和 12 均含有桥连的噻基配体，该配体以 η5-方式与一个锰原子键合。通过单晶X射线衍射研究确定了这些新复合物中的八个分子的结构，从而允许对配位配体的排布进行详细分析。