Department of Chemistry, Indian Institute of Technology Madras, Chennai 600 036, India.
Chemistry. 2010 Oct 4;16(37):11357-66. doi: 10.1002/chem.201001208.
Reaction of [1,2-(CpRuH)(2)B(3)H(7)] (1; Cp=η(5)-C(5)Me(5)) with [Mo(CO)(3)(CH(3)CN)(3)] yielded arachno-[(CpRuCO)(2)B(2)H(6)] (2), which exhibits a butterfly structure, reminiscent of 7 sep B(4)H(10). Compound 2 was found to be a very good precursor for the generation of bridged borylene species. Mild pyrolysis of 2 with [Fe(2)(CO)(9)] yielded a triply bridged heterotrinuclear borylene complex [(μ(3)-BH)(CpRuCO)(2)(μ-CO){Fe(CO)(3)}] (3) and bis-borylene complexes [{(μ(3)-BH)(CpRu)(μ-CO)}(2)Fe(2)(CO)(5)] (4) and [{(μ(3)-BH)(CpRu)Fe(CO)(3)}(2)(μ-CO)] (5). In a similar fashion, pyrolysis of 2 with [Mn(2)(CO)(10)] permits the isolation of μ(3)-borylene complex [(μ(3)-BH)(CpRuCO)(2)(μ-H)(μ-CO){Mn(CO)(3)}] (6). Both compounds 3 and 6 have a trigonal-pyramidal geometry with the μ(3)-BH ligand occupying the apical vertex, whereas 4 and 5 can be viewed as bicapped tetrahedra, with two μ(3)-borylene ligands occupying the capping position. The synthesis of tantalum borylene complex [(μ(3)-BH)(CpTaCO)(2)(μ-CO){Fe(CO)(3)}] (7) was achieved by the reaction of [(Cp*Ta)(2)B(4)H(9)(μ-BH(4))] [corrected] at ambient temperature with [Fe(2)(CO)(9)]. Compounds 2-7 have been isolated in modest yield as yellow to red crystalline solids. All the new compounds have been characterized in solution by mass spectrometry; IR spectroscopy; and (1)H, (11)B, and (13)C NMR spectroscopy and the structural types were unequivocally established by crystallographic analysis of 2-6.
[1,2-(CpRuH)(2)B(3)H(7)]（1；Cp=η(5)-C(5)Me(5)）与[Mo(CO)(3)(CH(3)CN)(3)]反应生成了 arachno-[(CpRuCO)(2)B(2)H(6)]（2），其呈现蝴蝶结构，类似于 7 sep B(4)H(10)。该化合物 2 被发现是生成桥联硼烯物种的非常好的前体。用[Fe(2)(CO)(9)]对 2 进行温和热解，得到了三桥联异核三硼烯配合物[(μ(3)-BH)(CpRuCO)(2)(μ-CO){Fe(CO)(3)}]（3）和双硼烯配合物[{(μ(3)-BH)(CpRu)(μ-CO)}(2)Fe(2)(CO)(5)]（4）和[{(μ(3)-BH)(CpRu)Fe(CO)(3)}(2)(μ-CO)]（5）。以类似的方式，用[Mn(2)(CO)(10)]对 2 进行热解，允许分离出μ(3)-硼烯配合物[(μ(3)-BH)(CpRuCO)(2)(μ-H)(μ-CO){Mn(CO)(3)}]（6）。化合物 3 和 6 均具有三角双锥几何形状，μ(3)-BH 配体占据顶点，而 4 和 5 可以看作是双帽四面体，两个 μ(3)-硼烯配体占据帽状位置。通过在环境温度下用[Fe(2)(CO)(9)]反应[(CpTa)(2)B(4)H(9)(μ-BH(4))]来合成 Ta 硼烯配合物[(μ(3)-BH)(Cp*TaCO)(2)(μ-CO){Fe(CO)(3)}]（7）。2-7 已作为黄色至红色结晶固体以中等产率分离出来。所有新化合物均通过质谱；红外光谱；(1)H、(11)B 和(13)C NMR 光谱在溶液中进行了表征，并通过 2-6 的晶体结构分析明确确定了结构类型。
