Selective Lithiation and Phosphane-Functionalization of [(η7-C7H7)Ti(η5-C5H5)] (Troticene) and Its Use for the Preparation of Early-Late Heterobimetallic Complexes,Journal of the American Chemical Society

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Selective Lithiation and Phosphane-Functionalization of [(η7-C7H7)Ti(η5-C5H5)] (Troticene) and Its Use for the Preparation of Early-Late Heterobimetallic Complexes
Journal of the American Chemical Society ( IF 14.4 ) Pub Date : 2009-11-25 , DOI: 10.1021/ja9080056
Swagat K. Mohapatra ₁ , Susanne Büschel ₁ , Constantin Daniliuc ₁ , Peter G. Jones ₁ , Matthias Tamm ₁

Affiliation

The cycloheptatrienyl-cyclopentadienyl sandwich complex [(eta(7)-C(7)H(7))Ti(eta(5)-C(5)H(5))] (troticene) can be dilithiated (once at each ring) or selectively monolithiated, either at the seven- or five-membered ring, depending on the reaction conditions. Treatment of the resulting lithiotroticenes with ClPPh(2) afforded the corresponding troticenyl-phosphanes [(eta(7)-C(7)H(6)PPh(2))Ti(eta(5)-C(5)H(4)PPh(2))] (1), [(eta(7)-C(7)H(6)PPh(2))Ti(eta(5)-C(5)H(5))] (2), or [(eta(7)-C(7)H(7))Ti(eta(5)-C(5)H(4)PPh(2))] (3). The use of nBuLi/N,N',N',N'',N"-pentamethyldiethylenetriamine (pmdta) allowed us to isolate the lithium complexes [(eta(7)-C(7)H(6)Li)Ti(eta(5)-C(5)H(4)Li)] x pmdta (4) and [(eta(7)-C(7)H(7))Ti(eta(5)-C(5)H(4)Li)] x pmdta (5), which were structurally characterized by X-ray diffraction analyses. Reaction of the monophosphane 3 with Mo(CO)(6) and [(tht)AuCl] (tht = tetrahydrothiophene) afforded the heterobimetallic complexes [(3)Mo(CO)(5)] (6) and [(3)AuCl] (7) and also the trimetallic species [(3)(2)AuCl] (8). The reaction of trans-[PtCl(2)(SEt(2))(2)] with the diphosphane 1 led to the formation of cis-[(1)PtCl(2)] (9), whereas the complexes trans-[(2)(2)PtCl(2)] (10) and trans-[(3)(2)PtCl(2)] (11) were isolated by reaction of two equivalents of the monophosphanes 2 and 3 with trans-[PtCl(2)(SEt(2))(2)]. The X-ray crystal structures of 6-11 are also reported.

中文翻译：

[(η7-C7H7)Ti(η5-C5H5)] (Troticene) 的选择性锂化和磷烷官能化及其在制备早晚异双金属配合物中的用途

环庚三烯基-环戊二烯基夹心复合物 [(eta(7)-C(7)H(7))Ti(eta(5)-C(5)H(5))]（troticene）可以被二锂化（在每个环上一次) 或在七元环或五元环上选择性地单锂化，具体取决于反应条件。用 ClPPh(2) 处理所得的硫代三烯基得到相应的三烯基膦 [(eta(7)-C(7)H(6)PPh(2))Ti(eta(5)-C(5)H(4) )PPh(2))] (1), [(eta(7)-C(7)H(6)PPh(2))Ti(eta(5)-C(5)H(5))] (2 )，或 [(eta(7)-C(7)H(7))Ti(eta(5)-C(5)H(4)PPh(2))] (3)。nBuLi/N,N',N',N'',N"-五甲基二亚乙基三胺 (pmdta) 的使用使我们能够分离锂复合物 [(eta(7)-C(7)H(6)Li)Ti( eta(5)-C(5)H(4)Li)] x pmdta (4) 和 [(eta(7)-C(7)H(7))Ti(eta(5)-C(5)H (4)Li)] x pmdta (5)，通过 X 射线衍射分析对其结构进行了表征。单膦 3 与 Mo(CO)(6) 和 [(tht)AuCl]（tht = 四氢噻吩）反应得到异双金属配合物 [(3)Mo(CO)(5)] (6) 和 [(3)AuCl ] (7) 以及三金属物种 [(3)(2)AuCl] (8)。trans-[PtCl(2)(SEt(2))(2)] 与双膦 1 的反应导致形成 cis-[(1)PtCl(2)] (9)，而复合物 trans-[ (2)(2)PtCl(2)] (10) 和反式-[(3)(2)PtCl(2)] (11) 通过两当量的单膦 2 和 3 与反式-[PtCl (2)(SEt(2))(2)]。还报道了 6-11 的 X 射线晶体结构。trans-[PtCl(2)(SEt(2))(2)] 与双膦 1 的反应导致形成 cis-[(1)PtCl(2)] (9)，而复合物 trans-[ (2)(2)PtCl(2)] (10) 和反式-[(3)(2)PtCl(2)] (11) 通过两当量的单膦 2 和 3 与反式-[PtCl (2)(SEt(2))(2)]。还报道了 6-11 的 X 射线晶体结构。trans-[PtCl(2)(SEt(2))(2)] 与双膦 1 的反应导致形成 cis-[(1)PtCl(2)] (9)，而复合物 trans-[ (2)(2)PtCl(2)] (10) 和反式-[(3)(2)PtCl(2)] (11) 通过两当量的单膦 2 和 3 与反式-[PtCl (2)(SEt(2))(2)]。还报道了 6-11 的 X 射线晶体结构。

更新日期：2009-11-25

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