Di‐ and Trinuclear Alkyne‐ and Vinylidenerhodium(I) Complexes Including the X‐ray Crystal Structure of a Dendrimer‐Like Rh3 Compound
Di‐ and Trinuclear Alkyne‐ and Vinylidenerhodium(I) Complexes Including the X‐ray Crystal Structure of a Dendrimer‐Like Rh3 Compound
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双核和三核炔烃和亚乙烯基铑 (I) 配合物，包括树枝状大分子 Rh3 化合物的 X 射线晶体结构
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发表时间：
1998
期刊：
影响因子：
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通讯作者：
Olaf Gevert
中科院分区：
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作者：
H. Werner;P. Bachmann;M. Laubender;Olaf Gevert
二聚体[RhClL 2]2（1; L = PiPr 3）与1，3，5-C6 H3（C = CH）3反应，在初始步骤中得到三（炔）三铑化合物2，其在甲苯中在60 °C重排，得到异构体三（亚乙烯基）络合物3。用吡啶处理2或3得到三核三（炔基）三铑（III）配合物4。三甲硅烷基衍生物1，3，5-C6 H3（C <$CSiMe3）3与1反应生成单核化合物5，其中只有一个C <$C键与Rh配位。二炔1，3-和1，2-C6 H4（CH = CH）2的行为类似于1，3，5-C6 H3（CH = CH）3，并且在用1处理后，首先产生双（炔）二铑络合物6和7，随后产生双（亚乙烯基）二铑异构体8和9。1，2-、1，3-和1，4-C6 H4（C = CSiMe 3）2与1的反应采取类似的过程，分别得到双（炔）和双（亚乙烯基）化合物10- 1,2和1,3 -15。以同样的方式，双核双（炔）和双（亚乙烯基）配合物16和17已经由1和萘衍生物1，5-C10 H6（C = CH）2制备。用X射线晶体学方法测定了化合物17和树枝状Rh 3化合物3的分子结构。
The dimer [RhClL2]2 (1; L = PiPr3) reacts with 1,3,5-C6H3(C≡CH)3 to give in the initial step the tris(alkyne)trirhodium compound 2, which rearranges in toluene at 60 °C to yield the isomeric tris(vinylidene) complex 3. Treatment of either 2 or 3 with pyridine affords the trinuclear tris(alkynyl)trihydridorhodium(III) complex 4. The trisilyl derivative 1,3,5-C6H3(C≡CSiMe3)3 reacts with 1 to form the mononuclear compound 5, in which only one of the C≡C bonds is coordinated to Rh. The diynes 1,3- and 1,2-C6H4(C≡CH)2 behave analogously to 1,3,5-C6H3(C≡CH)3 and upon treatment with 1 yield initially the bis(alkyne)dirhodium complexes 6 and 7 and subsequently the bis(vinylidene)dirhodium isomers 8 and 9. The reactions of 1,2-, 1,3-, and 1,4-C6H4(C≡CSiMe3)2 with 1 take a similar course and give the bis(alkyne) and bis(vinylidene) compounds 10–12 and 13–15, respectively. In the same way, the dinuclear bis(alkyne) and bis(vinylidene) complexes 16 and 17 have been prepared from 1 and the naphthalene derivative 1,5-C10H6(C≡CH)2. The molecular structures of 17 and of the dendrimer-like Rh3 compound 3 have been determined by X-ray crystallography.