Frogley Benjamin J, Hill Anthony F, Shang Rong, Sharma Manab, Willis Anthony C
Research School of Chemistry, The Australian National University, Canberra, ACT 2601, Australia.
Department of Chemistry, Graduate School of Science, Hiroshima University, Hiroshima, Japan.
Chemistry. 2020 Jul 17;26(40):8819-8827. doi: 10.1002/chem.202000635. Epub 2020 Jun 29.
The "CPNR" ligand may be viewed as being isolobal with fulminate, CNO; however, attempts to prepare a complex of such a ligand resulted instead in a range of novel imino and aminophosphinocarbyne complexes. Sequential treatment of [Mo(≡CBr)(CO) (Tp*)] (Tp*=hydrotris(dimethylpyrazolyl)borate) with nBuLi and ClP=NMes* (Mes*=C H tBu -2,4,6) afforded mixtures of the complexes [Mo(≡CPnBuNHMes*)(CO) (Tp*)] and traces of the bimetallic products [Mo {μ -C P O(NHMes) }(CO) (Tp*) ] and [Mo (μ -C PNHMes)(CO) (Tp*) ]. The reaction of [W(≡CBr)(CO) (Tp*)] with nBuLi and ClP=NMes* afforded predominantly the mononuclear carbyne [W{≡CP(=NMes*)nBu })(CO) (Tp*)] and traces of the binuclear complex [W (μ-C PNHMes)(CO) (Tp*) ] which is also obtained when tBuLi is used. Although not isolable, the intended complexes [M(≡CPNMes*)(CO) (Tp*)] could be generated in situ and spectroscopically characterized via the reactions of the stannyl carbynes [M(≡CSnnBu )(CO) (Tp*)] and ClP=NMes*. The preceding observations are mechanistically interpreted with reference to a computational interrogation of the model complex [Mo(≡CP=NCH )(CO) (Tp*)], the LUMO of which has considerable phosphorus character.
“CPNR”配体可被视为与雷酸盐（CNO）等瓣异构；然而，尝试制备这种配体的配合物却得到了一系列新型亚氨基和氨基膦卡宾配合物。用正丁基锂和ClP=NMes*（Mes* = C6H2tBu -2,4,6）对[Mo(≡CBr)(CO) (Tp*)]（Tp* = 氢三（二甲基吡唑基）硼酸盐）进行连续处理，得到了配合物[Mo(≡CPnBuNHMes*)(CO) (Tp*)]的混合物以及痕量的双金属产物[Mo {μ -C P O(NHMes) }(CO) (Tp*) 2]和[Mo 2(μ -C PNHMes)(CO) (Tp*) 2]。[W(≡CBr)(CO) (Tp*)]与正丁基锂和ClP=NMes的反应主要生成单核卡宾[W{≡CP(=NMes)nBu })(CO) (Tp*)]以及痕量的双核配合物[W 2(μ-C PNHMes)(CO) (Tp*)]，使用叔丁基锂时也会得到该双核配合物。尽管无法分离得到，但预期的配合物[M(≡CPNMes*)(CO) (Tp*)]可通过锡烷基卡宾[M(≡CSnnBu )(CO) (Tp*)]与ClP=NMes的反应原位生成并通过光谱进行表征。上述观察结果通过对模型配合物[Mo(≡CP=NCH3)(CO) (Tp)]的计算研究从机理上进行了解释，该模型配合物的最低未占分子轨道具有相当大的磷特征。
