Self-assembly of isomeric clamshell dimers of platinum(II).
Self-assembly of isomeric clamshell dimers of platinum(II).
复制标题
铂(II) 异构蛤壳二聚体的自组装。
作者：
Matthew S. McCready;R. Puddephatt
报道了异构有机铂蛤壳二聚体 [Pt(2)Me(2)(μ(2)-κ(3)-6-dppd)(2)](2+), 6-dppd = 1,4-di-2-pyridyl-5,6,7,8,9,10-hexaHydrcycloocta[d]pyridazine 的受控合成。利用铂 (II) 的缓慢顺反异构化，通过单核前体的自组装选择性地形成新配合物。因此endo-[PtClMe(κ(2)-6-dppd)]与AgOTf反应得到endo,endo-[Pt(2)Me(2)(μ(2)-κ(3)-6-dppd)(2)](2+)，而[PtMe(2)(κ(2)-6-dppd)]与HOTf在溶剂S = Me(2)C=O或MeCN中反应首先得到以下混合物exo-和endo-[PtMe(S)(κ(2)-6-dppd)](+)，然后通过溶剂损失，得到exo、exo-和endo、endo-[Pt(2)Me(2)(μ(2)-κ(3)-6-dppd)(2)](2+)的混合物。内，内异构体在溶液中缓慢异构化为更稳定的外，外异构体。 PPh(3) 与内型-[PtClMe(κ(2)-6-dppd)] 反应得到内型和外型-[PtMe(PPh(3))(κ(2)-6-dppd)](+) 的混合物，但与外型，外型-[Pt(2)Me(2)(μ(2)-κ(3)-6-dppd)(2)](2+) 反应得到选择性外切-[PtMe(PPh(3))(κ(2)-6-dppd)](+)，保留立体化学。报道了蛤壳二聚体和关键前体的结构，并通过实验和 DFT 计算研究了平衡。
The controlled synthesis of isomeric organoplatinum clamshell dimers [Pt(2)Me(2)(μ(2)-κ(3)-6-dppd)(2)](2+), 6-dppd = 1,4-di-2-pyridyl-5,6,7,8,9,10-hexahydrocycloocta[d]pyridazine, is reported. The new complexes are formed selectively by self-assembly from mononuclear precursors, taking advantage of the slow cis-trans isomerization at platinum(II). Thus reaction of endo-[PtClMe(κ(2)-6-dppd)] with AgOTf gave endo,endo-[Pt(2)Me(2)(μ(2)-κ(3)-6-dppd)(2)](2+), while the reaction of [PtMe(2)(κ(2)-6-dppd)] with HOTf in solvent S = Me(2)C=O or MeCN gave first a mixture of exo- and endo-[PtMe(S)(κ(2)-6-dppd)](+) and then, by loss of solvent, a mixture of exo,exo- and endo,endo-[Pt(2)Me(2)(μ(2)-κ(3)-6-dppd)(2)](2+). The endo,endo isomer slowly isomerized to the more stable exo,exo isomer in solution. Reaction of PPh(3) with endo-[PtClMe(κ(2)-6-dppd)] gave a mixture of endo- and exo-[PtMe(PPh(3))(κ(2)-6-dppd)](+) but reaction with exo,exo-[Pt(2)Me(2)(μ(2)-κ(3)-6-dppd)(2)](2+) gave exo-[PtMe(PPh(3))(κ(2)-6-dppd)](+) selectively, with retention of stereochemistry. The structures of the clamshell dimers and of key precursors are reported and equilibria are studied both experimentally and by DFT calculations.
影响因子：
15
作者：
Chi, KW;Addicott, C;Stang, PJ
通讯作者：
Stang, PJ
影响因子：
62.1
作者：
Chakrabarty, Rajesh;Mukherjee, Partha Sarathi;Stang, Peter J.
通讯作者：
Stang, Peter J.