General Strategy for the Synthesis of Rigid Weak-Link Approach Platinum(II) Complexes: Tweezers, Triple-Layer Complexes, and Macrocycles

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• 作者：Robert D. Kennedy ; Charles W. Machan ; C. Michael McGuirk ; Mari S. Rosen ; Charlotte L. Stern ; Amy A. Sarjeant ; Chad A. Mirkin
• 刊名：Inorganic Chemistry
• 出版年：2013
• 出版时间：May 20, 2013
• 年：2013
• 卷：52
• 期：10
• 页码：5876-5888
• 全文大小：621K
• 年卷期：v.52,no.10(May 20, 2013)
• ISSN：1520-510X

文摘

Air-stable, heteroligated platinum(II) weak-link approach (WLA) tweezer and triple-layer complexes that possess P,X鈥揂ryl hemilabile ligands (P^ = Ph₂PCH₂CH₂鈥? X = chalcoethers or amines) have been synthesized via the halide-induced ligand rearrangement (HILR) reaction, using a one-pot, partial chloride-abstraction method. The approach is general and works with a variety of phosphine-based hemilabile ligands; when a P,S鈥揚h ligand is used as the relatively strongly chelating ligand, heteroligated complexes are formed cleanly when an ether- (P,O鈥揚h), amine- (P,N鈥揚h₂), or fluorinated thioether-based (P,S鈥揅₆F₄H) hemilabile ligand is used as the weakly chelating counterpart. The HILR reaction has also been used to synthesize bisplatinum(II) macrocycles free of oligomeric material without having to resort to the high-dilution conditions typical for macrocycle synthesis. This approach is complementary to the traditional WLA to the synthesis of macrocyclic complexes which typically proceeds via fully closed, chloride-free intermediates. The structures of the complexes may be toggled between semiopen (with only one chelating ligand) and fully closed (with both ligands chelating) via the abstraction and addition of chloride.