STUDIES OF GERMANIUM-TRANSITION METAL BOND FORMATION

锗-过渡金属键形成的研究

• 批准号: 10640529
• 负责人: MOCHIDA Kunio
• 金额: $ 2.11万
• 依托单位: Gakushuin University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 1998
• 资助国家: 日本
• 起止时间: 1998 至 1999
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-10640529/
• 关键词: Bis-germylaton; Digermylpatinum complex; Reductive elimination; T-type intermediate; Germanium-germanium bond; acetylenes; ジゲルマン; 白金錯体; 挿入反応; ゲルマニウム-白金結合; X線結晶構造解析; ねじれ構造; 酸化的付加

Hexamethyldigermanes reacted with various alkynes in the presence of platinum complexes (0) at 120℃ to afford Z-bis(germyl)ethenes in moderate to good yields. Bis(germyl)platinum complexes (II) having various tertiary phosphine ligands have been prepared as a model of a key intermediate in the catalytic bis-germylation of alkynes and their structures have been established by spectroscopic methods and X-ray crystallography. Bis(germyl)platinum complexes reacted with phenylacctylene to give the corresponding insertion complexes, germyl(germylvinyl)platinum species, whose structures have been determined by spectroscopic and X-ray analysis. Germyl(germylvinyl)platinum complexes were found to liberate a bis-germylation product of the alkyne on heating. The result supports the mechanism involving oxidative addition of a digermane to Pt(0) complex, insertion of alkynes into one of the two Pt-Ge bonds to give a germyl(germylvinyl)platinum species, and reductive elimination of the bis-germylation product of the alkynes.

在铂配合物（0）存在下，六甲基二锗烷与各种炔在120℃下反应，以中等至良好的产率得到Z-双（锗基）乙烯。本文报道了一种具有多种叔膦配体的双（甲锗基）铂配合物（Ⅱ），它是催化炔烃双甲锗化反应的关键中间体，并通过光谱和X-射线晶体学方法确定了它们的结构。双（甲锗基）铂配合物与苯乙炔反应，得到相应的插入配合物甲锗基（甲锗基乙烯基）铂物种，其结构经光谱和X射线衍射分析确定。发现锗基（锗基乙烯基）铂络合物在加热时释放炔的双锗化产物。结果支持的机制，涉及氧化加成的二锗烷铂（0）配合物，插入到两个Pt-Ge键之一的炔，得到甲锗基（甲锗基乙烯基）铂物种，和还原消除的双甲锗化产物的炔。

项目成果

持田 邦夫: "Thermal Ring Contraction of 1,2-Digermacyclohexadienes Coordinated with Iron Tricarbonyl Fragment"Chem.Lett.,. 991-992 (1998)

Kunio Mochida：“1,2-二甲环己二烯与三羰基铁片段协调的热环收缩”Chem.Lett.，991-992（1998）

持田邦夫: "Thermal Ring Contraction of 1.2-Digermacyclohexadienes Coordinated with lron Tricarbonyl Fragment" Chem.Lett.991-992 (1998)

Kunio Mochida：“1.2-二甲环己二烯与铁三羰基片段协调的热环收缩”Chem.Lett.991-992 (1998)

持田邦夫: "Thermal Ring Contraction of 1・2-Digermacyclohexadienes coordinated with Iron Tricarbonyl Fragment"Chem. Lett. 991-992 (1998)

Kunio Mochida：“1·2-二甲环己二烯与三羰基铁片段协调的热环收缩”Chem. 991-992 (1998)

Kunio Mochida: "Thermal Ring Contraction of 1,2-Digermacyclohexadienes Coordinated with Iron Tricarbonyl Fragment"Chem. Lett.. 991-992 (1998)

Kunio Mochida：“1,2-二甲环己二烯与三羰基铁片段配合的热环收缩”Chem。