DeBackere John R, Mercier Hélène P A, Schrobilgen Gary J
Department of Chemistry, McMaster University , Hamilton, Ontario L8S 4M1, Canada.
Inorg Chem. 2015 Oct 19;54(20):9989-10000. doi: 10.1021/acs.inorgchem.5b01769. Epub 2015 Sep 28.
Reactions of Hg(OTeF5)2 with excess amounts of NSF3 at 0 °C result in the formation of NSF3 adducts having the compositions [Hg(OTeF5)2·N≡SF3]∞ (1), [Hg(OTeF5)2·2N≡SF3]2 (2), and Hg3(OTeF5)6·4N≡SF3 (3). When the reactions are carried out at room temperature, oxygen/fluorine metatheses occur yielding the F2OSN- derivatives [Hg(OTeF5)(N═SOF2)·N≡SF3]∞ (4) and [Hg3(OTeF5)5(N═SOF2)·2N≡SF3]2 (5). The proposed reaction pathway leading to F2OSN- group formation occurs by nucleophilic attack by a F5TeO- group at the sulfur(VI) atom of NSF3, followed by TeF6 elimination. Tellurium hexafluoride formation was confirmed by (19)F NMR spectroscopy. The NSF3 molecules are terminally N-coordinated to mercury, whereas the F2OSN- ligands are N-bridged to two mercury atoms. The compound series was characterized by low-temperature single-crystal X-ray diffraction and low-temperature Raman spectroscopy. Several structural motifs are observed within this structurally diverse series. These include the infinite chain structures of the related compounds, 1 and 4; 2, a dimeric structure which possesses an (HgO(μ))2 ring at its core; 3, a structure based on a cage comprised of a (HgO(μ))3 ring that is capped on each face by μ(3)-oxygen bridged F5TeO- groups; and 5, a dimeric structure possessing two distorted (Hg3O2N) rings that are formally derived from 3 by replacement of a F5TeO- group by a F2OSN- group in each ring. Quantum-chemical calculations were carried out to gain insight into the bonding of the μ(3)-oxygen bridged teflate groups observed in structure 3. Compounds 1-5 represent a novel class of neutral transition metal complexes with NSF3, providing the first examples of NSF3 coordination to mercury. Compounds 4 and 5 also provide the only examples of F2OSN- derivatives of mercury that have been characterized by single-crystal X-ray diffraction.
Hg(OTeF5)2与过量的NSF3在0 °C下反应，生成组成为[Hg(OTeF5)2·N≡SF3]∞ (1)、[Hg(OTeF5)2·2N≡SF3]2 (2)和Hg3(OTeF5)6·4N≡SF3 (3)的NSF3加合物。当反应在室温下进行时，会发生氧/氟交换反应，生成F2OSN-衍生物[Hg(OTeF5)(N═SOF2)·N≡SF3]∞ (4)和[Hg3(OTeF5)5(N═SOF2)·2N≡SF3]2 (5)。导致形成F2OSN-基团的反应途径是通过F5TeO-基团对NSF3的硫(VI)原子进行亲核攻击，随后消除TeF6。通过(19)F NMR光谱证实了六氟化碲的形成。NSF3分子以末端N配位到汞上，而F2OSN-配体则通过N桥连到两个汞原子上。该化合物系列通过低温单晶X射线衍射和低温拉曼光谱进行了表征。在这个结构多样的系列中观察到了几种结构基序。这些包括相关化合物1和4的无限链结构；2是一种二聚体结构，其核心具有一个(HgO(μ))2环；3是一种基于由(HgO(μ))3环组成的笼状结构，每个面上都由μ(3)-氧桥连的F5TeO-基团封顶；5是一种二聚体结构，具有两个扭曲的(Hg3O2N)环，这些环正式地由3通过在每个环中用一个F2OSN-基团取代一个F5TeO-基团而衍生而来。进行了量子化学计算，以深入了解在结构3中观察到的μ(3)-氧桥连的碲酸根基团的键合。化合物1 - 5代表了一类新型的与NSF3形成的中性过渡金属配合物，提供了NSF3与汞配位的首个实例。化合物4和5还提供了唯一通过单晶X射线衍射表征的汞的F2OSN-衍生物实例。
