Synthesis, Structure, and Reactivity of Tungsten Acetylide–Germylene Complexes
Synthesis, Structure, and Reactivity of Tungsten Acetylide–Germylene Complexes
复制标题
乙炔钨-甲锗烷配合物的合成、结构和反应性
DOI：
10.1021/om4000264
复制
发表时间：
2013
期刊：
影响因子：
2.8
通讯作者：
Eunsang Kwon
中科院分区：
文献类型：
--
作者：
H. Sakaba;Y. Arai;Kensei Suganuma;Eunsang Kwon
用Cp*(CO)2W(NCMe)Me与Ph2HGeC≡CR （R = SiMe3, CMe3）反应合成了新型乙酰基乙烯配合物Cp*(CO)2W(GePh2)(CCR) （7a, R = SiMe3; 7b, R = CMe3）。x射线晶体分析显示，与之前报道的乙炔-硅烯配合物Cp*(CO)2W(SiPh2)（CCSiMe3）相比，7a的乙炔-钨相互作用明显增加，乙炔-乙炔相互作用明显减少(1)。配合物7a、b与丙酮反应生成六元环乙烯配合物Cp*(CO)2W = C = C(R)CMe2OGePh2 (8a, R = SiMe3; 8b, R = CMe3)，类似于1生成Cp*(CO)2W = C = C(SiMe3)CMe2OSiPh2(2)的情况。在4-（二甲氨基）吡啶（DMAP）存在下，配合物8a、b生成反式和顺式DMAP稳定的germylene acetide配合物Cp*(CO)2W(GePh2·DMAP)(CCR)（反式和顺式-9a， R = SiMe3；反式和顺式-9b， R = CMe3）和丙酮，表现出与硅类似物2不同的反应活性。配合物cis-9a，b…
The novel acetylide–germylene complexes Cp*(CO)2W(GePh2)(CCR) (7a, R = SiMe3; 7b, R = CMe3) were synthesized by the reactions of Cp*(CO)2W(NCMe)Me with Ph2HGeC≡CR (R = SiMe3, CMe3). X-ray crystal analysis of 7a revealed significantly increased germylene–tungsten and decreased germylene–acetylide interactions in comparison to the corresponding interactions in the previously reported acetylide–silylene complex Cp*(CO)2W(SiPh2)(CCSiMe3) (1). Complexes 7a,b reacted with acetone to give the six-membered cyclic vinylidene complexes Cp*(CO)2W═C═C(R)CMe2OGePh2 (8a, R = SiMe3; 8b, R = CMe3) by acetone insertion reaction, similar to the case of 1 affording Cp*(CO)2W═C═C(SiMe3)CMe2OSiPh2 (2). In the presence of 4-(dimethylamino)pyridine (DMAP), complexes 8a,b gave trans- and cis-DMAP-stabilized germylene acetylide complexes Cp*(CO)2W(GePh2·DMAP)(CCR) (trans- and cis-9a, R = SiMe3; trans- and cis-9b, R = CMe3) and acetone, showing a reactivity different from that of the silicon analogue 2. Complexes cis-9a,b were iso...