Platinum-Catalyzed Bis-Germylation of Alkynes with Organodigermanes and Cyclic Oligogermanes
Platinum-Catalyzed Bis-Germylation of Alkynes with Organodigermanes and Cyclic Oligogermanes
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铂催化的炔烃与有机二锗烷和环状低聚锗烷的双锗化反应
DOI：
10.1246/bcsj.74.123
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发表时间：
2001
影响因子：
4
通讯作者：
A. Yamamoto
中科院分区：
文献类型：
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作者：
K. Mochida;Tohru Wada;Kaoru Suzuki;Wakako Hatanaka;Yuriko Nishiyama;M. Nanjo;A. Sekine;Y. Ohashi;M. Sakamoto;A. Yamamoto
六甲基二癸烷（Me3GeGeMe3）在铂配合物存在下与各种炔在120℃下反应，以中高收率得到z - 1,2-二（germyl）乙烯。端炔的反应活性高于内炔。[Pt(acac)2]和[Pt(dba)2]是高效催化剂，而[Pt(PPh3)4]、[PtCl2(PPh3)2]和[Pt(dba)2]-亚磷酸酯则是无活性催化剂。四元和六元环低聚物，如十二甲基环六烯（Me2Ge）6，在铂催化剂存在下与炔反应，产率约为30%，得到1,4-二甲基环六烯-2,5-二烯。苯乙炔与1,2-二二元环己-3,5-二烯反应得到相应的1,4-二二元环己-2,5,7-三烯，产率为93%。制备了具有多种叔膦配体的双（germyl）铂配合物，作为上述炔烃催化双芽化反应的关键中间体模型，并通过光谱方法和x射线晶体学确定了其结构。Bi……
Hexamethyldigermane, Me3GeGeMe3, reacted with various alkynes in the presence of platinum complexes at 120 °C to afford Z–1,2-bis(germyl)ethenes in moderate to good yields. Terminal alkynes exhibit higher reactivities than internal ones. [Pt(acac)2] and [Pt(dba)2] serve as efficient catalysts, while [Pt(PPh3)4], [PtCl2(PPh3)2], and [Pt(dba)2]-phosphite were found to be inactive. Four- and six-membered cyclic oligogermanes, such as dodecamethylcyclohexagermane, (Me2Ge)6, reacted with alkynes in the presence of platinum catalysts to yield 1,4-digermacyclohexa-2,5-dienes in ca. 30% yield. The reactions of phenylacetylene with 1,2-digermacyclohexa-3,5-dienes afforded the corresponding 1,4-digermacycloocta-2,5,7-trienes in 93% yield. Bis(germyl)platinum complexes having various tertiary phosphine ligands have been prepared as models of a key intermediate in the above mentioned catalytic bis-germylation of alkynes, and their structures have been established by spectroscopic methods and X-ray crystallography. Bi...