Yadav Sandeep, Kumar Rohit, Vipin Raj K, Yadav Prashant, Vanka Kumar, Sen Sakya S
Inorganic Chemistry and Catalysis Division, CSIR-National Chemical Laboratory, Dr. Homi Bhabha Road, Pashan, Pune, 411008, India.
Academy of Scientific and Innovative Research (AcSIR), Ghaziabad, 201002, India.
Chem Asian J. 2020 Oct 1;15(19):3116-3121. doi: 10.1002/asia.202000807. Epub 2020 Sep 4.
Despite the explosive growth of germylene compounds as ligands in transition metal complexes, there is a modicum of precedence for the germylene zinc complexes. In this work, the synthesis and characterization of new germylene zinc complexes [PhC(NtBu) Ge{N(SiMe ) }→ZnX ] (X= Br (2) and I (3)) supported by (benz)-amidinato germylene ligands are reported. The solid-state structures of 2 and 3 have been validated by single-crystal X-ray diffraction studies, which revealed the dimeric nature of the complexes, with distorted tetrahedral geometries around the Ge and Zn center. DFT calculations reveal that the Ge-Zn bonds in 2 and 3 are dative in nature. The reaction of 2 with elemental sulfur resulted in the first structurally characterized germathione stabilized ZnBr complexes PhC(NtBu) Ge(=S){N(SiMe ) }→ZnBr (5). Therefore, the Ge=S in 5 is in-between Ge-S single and Ge=S double bond length, owing to the coordination of a sulfur lone pair of electrons to ZnBr .
尽管亚锗烯化合物作为过渡金属配合物中的配体呈爆发式增长，但亚锗烯锌配合物的先例却很少。在这项工作中，报道了由（苯）脒基亚锗烯配体支持的新型亚锗烯锌配合物[PhC（NtBu）Ge{N（SiMe）}→ZnX]（X = Br（2）和I（3））的合成与表征。通过单晶X射线衍射研究验证了2和3的固态结构，结果表明配合物具有二聚体性质，Ge和Zn中心周围的几何形状为扭曲的四面体。密度泛函理论计算表明，2和3中的Ge-Zn键本质上是配位键。2与元素硫反应生成了首个结构表征的亚锗硫醇稳定的ZnBr配合物PhC（NtBu）Ge（=S）{N（SiMe）}→ZnBr（5）。因此，由于硫孤对电子与ZnBr配位，5中的Ge=S键长介于Ge-S单键和Ge=S双键之间。
