1，1′─［四甲基二硅撑］双（环戊二烯基三羰基钨配合物）的合成及反应  

SYNTHESIS OF 1 , 1'- (TETRAMETHYL DISILANDIYL )BIS [CYCLOPENTADIENYLTRICARBONYL TUNGSTEN COMPLEXES]

作　　者：万一千[1] 周秀中[1] 刘伟文[1] 

机构地区：[1]南开大学化学系,天津教育学院物理系

出　　处：《南开大学学报（自然科学版）》1994年第4期94-96,104,共4页Acta Scientiarum Naturalium Universitatis Nankaiensis

摘　　要：１，２－二环戊二烯基四甲基二硅烷与丁基锂作用生成［四甲基二硅撑］双（环戊二烯基负离子盐），后者随即与六羰基钨反应形成１，１－［四甲基二硅撑］双［环戊二烯基三羰基钨负离子盐］，（Ｍｅ２ＳｉＳｉＭｅ２）·［Ｃｐ′（ＣＯ）３Ｗ－］２·２Ｌｉ＋（Ｉ）．（Ｉ）分别与六种卤化物反应，生成在钨原子上引入取代基的产物：（Ｍｅ２ＳｉＳｉＭｅ２）．［Ｃｐ′Ｗ（ＣＯ）３Ｒ］２，（Ｒ：Ｍｅ，Ｃ２Ｈ５，２；ＰｈＣＨ２，３；ＣＨ２ＣＯＯＣ２Ｈ５，４；ＣＨ３ＣＯ，５；Ｐ３ｈＳｎ，６）．（Ｉ）用醋酸处理后，随即分别与ＣＣｌ４，ＮＢＳ及Ｉ２作用，生成相应的钨卤化物，（Ｍｅ２ＳｉＳｉＭｅ２）［Ｃｐ′Ｗ（ＣＯ）３Ｘ］２，（Ｘ：Ｃ１，８；Ｂｒ，９；Ｉ，１０），（Ｉ）与Ｆｅ３＋／Ｈ３Ｏ＋作用发生氧化偶联，生成双核Ｗ－Ｗ键产物（Ｍｅ２ＳｉＳｉＭｅ２）［Ｃｐ′Ｗ（ＣＯ）３］２，１１．（Ｃｐ′＝Ｃ５Ｈ４）The reaction of tetramethyldisilandiyl biscyclopentadienyl dianion with W (CO)6 produced 1, 1'- (Tetramethyldisilandiyl )bis [Cyclopentadienyl tricarbonyl Tungsten dianion ] , (Me2SiSiMe2 )[C5H4W (CO)3]2-· 2Li + (I). 1 reacted respectively with variant halides to yield the corresponding tungsten derivatives (Me2SiSiMe2)[C5H4W(CO)3R]2,( R : Me, 1; C2H5, 2; PhCH2, 3; CH2COOC2H5, 4; CH3CO, 5;Ph3Sn, 6 ) . 1 reacted with HOAc,was reacted with CCl4 , NBS or I2 and afforded the corresponding tungsten halides (R:CL, 8; Br, 9 : I , 10). The reaction of 1 with Fe3+/H3O+ yielded the oxidative coupling dinuclear complex, (Me2SiSiMe2)[C5H4W (CO)3]2, (11). The structures characterized by elemental analyses, IR and 1HNMR spectra.

关 键 词：四甲基二硅撑基 羰基钨 双核 钨络合物 

分 类 号：O614.613[理学—无机化学]