title: General strategy for the synthesis of rigid weak-link approach platinum(II) complexes: tweezers, triple-layer complexes, and macrocycles.
abstract: Air-stable, heteroligated platinum(II) weak-link approach (WLA) tweezer and triple-layer complexes that possess P,X-Aryl hemilabile ligands (P^ = Ph2PCH2CH2-, 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-Ph ligand is used as the relatively strongly chelating ligand, heteroligated complexes are formed cleanly when an ether- (P,O-Ph), amine- (P,N-Ph2), or fluorinated thioether-based (P,S-C6F4H) 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.
authors: Department of Chemistry and International Institute for Nanotechnology, Northwestern University, 2145 Sheridan Road, Evanston, Illinois 60208, United States.
authors: Robert D
authors: RD
authors: Kennedy
authors: Charles W
authors: CW
authors: Machan
authors: C Michael
authors: CM
authors: McGuirk
authors: Mari S
authors: MS
authors: Rosen
authors: Charlotte L
authors: CL
authors: Stern
authors: Amy A
authors: AA
authors: Sarjeant
authors: Chad A
authors: CA
authors: Mirkin
mesh_terms: D018360:Crystallography, X-Ray; D047028:Macrocyclic Compounds / Q000138:chemical synthesis* / Q000737:chemistry; D008958:Models, Molecular; D015394:Molecular Structure; D009944:Organoplatinum Compounds / Q000138:chemical synthesis* / Q000737:chemistry
chemical_list: D047028:Macrocyclic Compounds; D009944:Organoplatinum Compounds