Institut für Anorganische und Analytische Chemie, Technische Universität Carolo-Wilhelmina, Hagenring 30, 38106 Braunschweig, Germany.
J Am Chem Soc. 2009 Nov 25;131(46):17014-23. doi: 10.1021/ja9080056.
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.
环庚三烯基-环戊二烯夹心配合物 [(η(7)-C(7)H(7))Ti(η(5)-C(5)H(5))]（troticene）可被双锂化（每个环一次）或选择性单锂化，具体取决于反应条件。所得的双锂troticenes 与 ClPPh(2)反应得到相应的 troticenyl-膦 [(η(7)-C(7)H(6)PPh(2))Ti(η(5)-C(5)H(4)PPh(2))] (1)、[(η(7)-C(7)H(6)PPh(2))Ti(η(5)-C(5)H(5))] (2) 或 [(η(7)-C(7)H(7))Ti(η(5)-C(5)H(4)PPh(2))] (3)。使用 nBuLi/N,N',N',N'',N"-五甲基二亚乙基三胺 (pmdta) 可以分离出锂配合物 [(η(7)-C(7)H(6)Li)Ti(η(5)-C(5)H(4)Li)] x pmdta (4) 和 [(η(7)-C(7)H(7))Ti(η(5)-C(5)H(4)Li)] x pmdta (5)，它们的结构通过 X 射线衍射分析进行了表征。单膦 3 与 Mo(CO)(6)和 [(tht)AuCl]（tht = 四氢噻吩）反应得到杂双金属配合物 [(3)Mo(CO)(5)] (6) 和 [(3)AuCl] (7) 以及三金属物种 [(3)(2)AuCl] (8)。反式-[PtCl(2)(SEt(2))(2)]与二膦 1 反应生成顺式-[(1)PtCl(2)] (9)，而配合物反式-[(2)(2)PtCl(2)] (10) 和反式-[(3)(2)PtCl(2)] (11) 则通过两个当量的单膦 2 和 3 与反式-[PtCl(2)(SEt(2))(2)]反应得到。6-11 的 X 射线晶体结构也有报道。
