From a Phosphaketenyl-Functionalized Germylene to 1,3-Digerma-2,4-diphosphacyclobutadiene.
From a Phosphaketenyl-Functionalized Germylene to 1,3-Digerma-2,4-diphosphacyclobutadiene.
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DOI：
10.1002/anie.201600701
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发表时间：
2016-04
影响因子：
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通讯作者：
Shenglai Yao;Y. Xiong;Tibor Szilvási;H. Grützmacher;M. Driess
中科院分区：
文献类型：
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作者：
Shenglai Yao;Y. Xiong;Tibor Szilvási;H. Grützmacher;M. Driess
第一个4π电子共振稳定的1，3-二锗-2，4-二磷杂环丁二烯[L（H）2Ge 2 P2] 4（L（H）=CH[CHNDipp] 2Dipp =2，以磷酰化的N-杂环锗烯[L（H）Ge-P=C=O] 2 a为原料，合成了β-双烯酮亚胺配体负载的四配位锗和二配位磷原子的Pr_2C_6H_3（6-（i）Pr_2C_6H_3）。磷炔酸钠（P-1C-ONa）与相应的氯锗撑[L（H）GeCl]的复分解反应1a.在室温紫外/维斯光照射下，2 a的P=C=O基团释放出CO，生成难以捉摸的锗-磷三键物种[L（H）Ge β P] 3 a，该物种自发二聚，以67%的产率得到可分离的黑色晶体4。值得注意的是，在二亚胺[Dipp-NC（（t）Bu）]2、双-N，P-杂环亚锗烷基[DippNC（（t）Bu）C（H）PGe]2的同时挤出下，从体积较大的取代的[L（tBu）Ge-P=C=O] 2 B b（L（tBu）=CH[C（（t）Bu）N-Dipp]2）释放CO。
The first 4π-electron resonance-stabilized 1,3-digerma-2,4-diphosphacyclobutadiene [L(H)2Ge2P2] 4 (L(H)=CH[CHNDipp]2 Dipp=2,6-(i)Pr2C6H3) with four-coordinate germanium supported by a β-diketiminate ligand and two-coordinate phosphorus atoms has been synthesized from the unprecedented phosphaketenyl-functionalized N-heterocyclic germylene [L(H)Ge-P=C=O] 2 a prepared by salt-metathesis reaction of sodium phosphaethynolate (P≡C-ONa) with the corresponding chlorogermylene [L(H)GeCl] 1 a. Under UV/Vis light irradiation at ambient temperature, release of CO from the P=C=O group of 2 a leads to the elusive germanium-phosphorus triply bonded species [L(H)Ge≡P] 3 a, which dimerizes spontaneously to yield black crystals of 4 as isolable product in 67% yield. Notably, release of CO from the bulkier substituted [L(tBu)Ge-P=C=O] 2 b (L(tBu)=CH[C((t)Bu)N-Dipp]2 ) furnishes, under concomitant extrusion of the diimine [Dipp-NC((t)Bu)]2, the bis-N,P-heterocyclic germylene [DippNC((t)Bu)C(H)PGe]2 5.