Inorg Chem. 2019 Feb 18;58(4):2346-2353. doi: 10.1021/acs.inorgchem.8b02759. Epub 2019 Feb 1.
The field of diborinane is sparsely explored area, and not many compounds are structurally characterized. The room-temperature reaction of [{CpRuCl(μ-Cl)}] (Cp = η-CMe) with Na[BH(SCHS)] yielded ruthenium dithioformato [{CpRu(μ,η-SCHS)}], 1, and 1-thioformyl-2,6-tetrahydro-1,3,5-trithia-2,6-diborinane complex, [(CpRu){(η-SCHS)CHS(BH)}], 2. To investigate the reaction pathway for the formation of 2, we carried out the reaction of [(BH)(CHS)], 3, with 1 that yielded compound 2. To the best of our knowledge, it appears that compound 2 is the first example of a ruthenium diborinane complex where the central six-membered ring [CBS] adopts the chair conformation. Furthermore, room temperature reaction of 1 with [BH·thf] resulted in the isolation of agostic-bis(σ-borate) complex, [CpRu(μ-H)BH(S-CH═S)], 4. Thermolysis of 4 with trace amount of tellurium powder led to formation of bis(bridging-boryl) complex, [{CpRu(μ,η-HBSCH)}], 5, via dimerization of 4 followed by dehydrogenation. Compound 5 can be considered as a bis(bridging-boryl) species, in which the boryl units are connected to two ruthenium atoms. Theoretical studies and chemical bonding analyses demonstrate the reason for exceptional reactivity and stability of these complexes.
二硼烷领域的研究尚处于起步阶段，结构得到明确表征的化合物也为数不多。[{CpRuCl(μ-Cl)}]（Cp=η-CMe）与 Na[BH(SCHS)]在室温下反应生成二硫代甲叉基二茂钌 [{CpRu(μ,η-SCHS)}]（1）和 1-硫代甲酰基-2,6-四氢-1,3,5-三噻-2,6-二硼烷配合物 [(CpRu){(η-SCHS)CHS(BH)}]（2）。为了研究 2 的形成反应途径，我们进行了 3 与 1 的反应，得到了化合物 2。据我们所知，2 似乎是首例采用椅式构象的钌二硼烷配合物。此外，1 与[BH·thf]在室温下反应得到了桥联双(σ-硼酸酯)配合物 [CpRu(μ-H)BH(S-CH═S)]（4）。4 与痕量碲粉的热解导致双(桥联硼基)配合物 [{CpRu(μ,η-HBSCH)}]（5）的形成，这是通过 4 的二聚化和脱氢反应实现的。化合物 5 可以被认为是一种桥联双硼基物种，其中硼基单元连接到两个钌原子上。理论研究和化学键分析证明了这些配合物具有异常反应活性和稳定性的原因。
