Terminal tungsten pnictide complex formation through pnictaethynolate decarbonylation
Terminal tungsten pnictide complex formation through pnictaethynolate decarbonylation
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DOI：
10.1039/c7cc06841g
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发表时间：
2017-10-04
影响因子：
4.9
通讯作者：
Cummins, Christopher C.
中科院分区：
文献类型：
--
作者：
Joost, Maximilian;Transue, Wesley J.;Cummins, Christopher C.
四（2，6-二异丙基苯酚）钨（IV）（1）已被证明是一个合适的平台，用于在用pnictaethynolate阴离子处理时脱羰基形成阴离子末端磷属元素化物络合物：氰酸根、2-磷炔酸根和2-胂炔酸根。这些转变构成了第一个例子的终端磷化物和砷化物络合物形成在过渡金属中心从OCP-和OCAs-，分别。磷化物和砷化物配合物也是第一个在四氢呋喃，全氧配体环境中分离出来的。利用自然键轨道（NBO）方法，根据σ键轨道和磷属元素孤对中的s轨道特征，测量了钨-183与氮-15或磷-31之间的标量NMR耦合常数.
Tungsten(IV) tetrakis(2,6-diisopropylphenoxide) (1) has been demonstrated to be a competent platform for decarbonylative formation of anionic terminal pnictide complexes upon treatment with pnictaethynolate anions: cyanate, 2-phosphaethynolate, and 2-arsaethynolate. These transformations constitute the first examples of terminal phosphide and arsenide complex formation at a transition metal center from OCP- and OCAs-, respectively. The phosphide and arsenide complexes are also the first to be isolated in a tetragonal, all-oxygen ligand environment. The scalar NMR coupling constants between tungsten-183 and nitrogen-15 or phosphorus-31 have been measured and contextualized using natural bond orbital (NBO) methods in terms of s orbital character in the sigma bonding orbital and pnictide lone pair.