The reaction of the labile triosmium cluster [Os₃(CO)₁₀(NCMe)₂] with tetramethylthiuram disulfide [(Me₂NCS₂)₂, tmtd] has been investigated at room temperature. Conducting the reaction under mild conditions has permitted the isolation of the three new polynuclear osmium complexes [Os₃(CO)₁₀{κ²(S,S)-S₂CNMe₂}₂] (1), [Os₄(CO)₁₂{κ²(S,S)-S₂CNMe₂}₂{μ₃-η¹(C),κ²(O,O)-CO₂)}(μ₃-S)] (2) and [Os₃(CO)₉{μ₃-η¹(C),κ¹(S)-SCNMe₂}{μ-κ¹(S)-SC(O)NMe₂}] (3) in 20, 16 and 10% yield, respectively, in addition to the known mononuclear complex [Os(CO)₂{κ²(S,S)-S₂CNMe₂}₂] (4) in 10% yield. The triosmium complex 1 has a linear arrangement of osmium atoms with each terminal osmium center containing a chelating Me₂NCS₂ ligand. The tetraosmium complex 2 also possesses a μ₃-CO₂ ligand in addition to capping sulfido and chelating Me₂NCS₂ ligands. Complex 3 contains an open triosmium core with the open Os···Os edge bridged by a Me₂NC(O)S ligand and a capping Me₂NCS ligand. A similar reaction between the unsaturated cluster [Os₃(CO)₁₀(μ-H)₂] and [(Me₂NCS₂)₂] yielded the triosmium complexes [Os₃(CO)₁₀{μ-κ¹(S)-S₂CNMe₂}(μ-H)] (5) and [Os₃(CO)₉{μ₃-κ²(S,S)-S₂CNMe₂}(μ-H)] (6) in addition to compounds 1 and 4 and the known hydroxyl cluster [Os₃(CO)₁₀(μ-OH)(μ-H)] (7) in 7, 14, 14, 10, and 6% yield, respectively. Both 5 and 6 possess a triosmium core, and the Me₂NCS₂ ligand acts in edge-bridging capacity in the former while it serves as a face-capping ligand in the latter. All new complexes have been characterized by combustion analyses and IR and NMR spectroscopies, and the solid-state structures of 1–3, and 6 have been established by X-ray crystallography. The bonding in clusters 1-3 and 6 has been examined by electronic structure calculations, and the thermodynamics for the formation of 1 and MeCN (two equiv) from [Os₃(CO)₁₀(MeCN)₂] and tmtd, relative to other chelated and bridged isomers of [Os₃(CO)₁₀(tmtd)] are discussed.

在室温下研究了不稳定的tri簇[Os ₃（CO）₁₀（NCMe）₂ ]与四甲基秋兰姆二硫化物[（Me ₂ NCS ₂）₂，tmtd]的反应。导电温和的条件下在反应允许的三个新的多核络合物锇的隔离了[Os ₃（CO）₁₀ {κ ²（S，S）-S ₂ CNME ₂ } ₂ ]（1），[O的₄（CO）₁₂ {κ ²（S，S）-S ₂ CNME ₂ } ₂ {μ₃ -η ¹（C），κ ²（O，O）-CO ₂）}（μ ₃ -S）]（2）和[O的₃（CO）₉ {μ ₃ -η ¹（C），κ ¹（S）-SCNMe ₂ } {μ-κ ¹（S）-SC（O）NME ₂ }]（3）在20，16和10％的产率，分别在除了已知的单核络合物[OS（CO）₂ {κ ²（S，S）-S ₂ CNME ₂ } ₂ ]（4）在10％的产率。os络合物1具有原子的线性排列，每个末端中心含有螯合的Me ₂ NCS ₂配体。所述tetraosmium复杂2还具有一个μ ₃ -CO ₂配体除了封盖硫代和螯合我₂ NCS _2个配体。配合物3包含一个开放的tri核，开放的Os···Os边缘由Me ₂ NC（O）S配体和一个封闭的Me ₂ NCS配体桥接。不饱和簇[Os ₃（CO）₁₀（μ-H）₂ ]与[（Me ₂ NCS ₂）₂〕得到的triosmium配合物[O的₃（CO）₁₀ {μ-κ ¹（S）-S ₂ CNME ₂ }（μ-H）]（5）和[O的₃（CO）₉ {μ ₃ -κ ²（S，S）-S ₂ CNMe ₂ }（μ-H）]（6）除了化合物1和4和已知的羟基簇[Os ₃（CO）₁₀（μ-OH）（μ-H）] （7）的产率分别为7、14、14、10和6％。两个5和6具有一triosmium芯，和ME₂ NCS ₂配体在前者中具有边缘桥接能力，而在后者中则充当了封端配体。所有新的复合物的特点是燃烧分析和IR和NMR光谱，和的固态结构1 - 3，和6已经通过X射线晶体学确定。在群集的结合1 - 3和6已经被电子结构计算检查和热力学的形成1和MeCN（2个当量）从[O的₃（CO）₁₀（MeCN中）₂ ]和TMTD，相对于其他[Os的螯合和桥接异构体_讨论3（CO）₁₀（tmtd）]。