低氧化态第14族元素卤化物的过渡金属介导的给体-受体配位
Transition metal-mediated donor-acceptor coordination of low-oxidation state Group 14 element halides.
作者信息
Swarnakar Anindya K, Ferguson Michael J, McDonald Robert, Rivard Eric
机构信息
Department of Chemistry, University of Alberta, 11227 Saskatchewan Drive, Edmonton, Alberta, Canada T6G 2G2.
出版信息
Dalton Trans. 2016 Apr 14;45(14):6071-8. doi: 10.1039/c5dt03018h.
The reactivity of tungsten carbonyl adducts of Group 14 element (Ge, Sn and Pb) dihalides towards the metal-based donors (η(5)-C5H5)Rh(PMe2Ph)2 and Pt(PCy3)2 was examined. When (η(5)-C5H5)Rh(PMe2Ph)2 was treated with the Lewis acid supported Ge(ii) complex, THF·GeCl2·W(CO)5, cyclopentadienyl ring activation occurred, whereas the analogous Lewis acidic units SnCl2·W(CO)5 and PbCl2 form direct adducts with the Rh complex to yield Rh-Sn and Rh-Pb dative bonds. Attempts to prepare metal coordinated element(ii) hydrides by adding hydride sources to the above mentioned rhodium-E(ii) halide complexes were unsuccessful; in each case insoluble products were formed along with regeneration of free (η(5)-C5H5)Rh(PMe2Ph)2. In a parallel study, ECl2·W(CO)5 (E = Ge or Sn) groups were shown to participate in E-Cl oxidation addition chemistry with (Cy3P)2Pt to give the formal Pt(ii) complexes ClPt(PCy3)2ECl·W(CO)5.
研究了第14族元素（锗、锡和铅）二卤化物的羰基钨加合物对金属基给体（η(5)-环戊二烯基）铑（二甲基苯基膦）₂和铂（三环己基膦）₂的反应活性。当用路易斯酸负载的锗（Ⅱ）配合物四氢呋喃·二氯化锗·五羰基钨处理（η(5)-环戊二烯基）铑（二甲基苯基膦）₂时，发生了环戊二烯基环活化，而类似的路易斯酸性单元二氯化锡·五羰基钨和二氯化铅与铑配合物形成直接加合物，生成铑-锡和铑-铅配位键。通过向上述铑-元素（Ⅱ）卤化物配合物中加入氢化物源来制备金属配位的元素（Ⅱ）氢化物的尝试未成功；在每种情况下，都会形成不溶性产物，同时游离的（η(5)-环戊二烯基）铑（二甲基苯基膦）₂再生。在一项平行研究中，二氯化E·五羰基钨（E = 锗或锡）基团被证明与（三环己基膦）₂铂参与E-Cl氧化加成反应，生成形式上的铂（Ⅱ）配合物氯铂（三环己基膦）₂ECl·五羰基钨。
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