Template-controlled synthesis of a planar [16]ane-P2C(NHC)2 macrocycle

Area of Science:

• Organometallic Chemistry
• Coordination Chemistry
• Synthetic Chemistry

Background:

• Tetraphosphine platinum(II) complexes are versatile precursors in coordination chemistry.
• Azidoethyl isocyanide serves as a valuable reagent for introducing specific functionalities.
• Carbene ligands, particularly N-heterocyclic carbenes (NHCs), play a crucial role in stabilizing metal centers and influencing reactivity.

Purpose of the Study:

• To investigate the reaction of tetraphosphine platinum(II) complexes with 2-azidoethyl isocyanide.
• To explore the subsequent reactivity of the resulting platinum-NHC complexes with phenyldivinylphosphine.
• To synthesize and characterize a novel macrocyclic platinum complex containing a [16]ane-P(2)C(NHC)(2) ligand.

Main Methods:

• Reaction of tetraphosphine platinum(II) complexes with 2-azidoethyl isocyanide in methanol.
• Substitution reactions of the intermediate platinum-NHC complexes with phenyldivinylphosphine.
• Intramolecular hydroamination to form the macrocyclic ligand.
• Characterization of the synthesized complexes using spectroscopic techniques (e.g., NMR, Mass Spectrometry) and X-ray crystallography.

Main Results:

• The reaction yielded platinum(II) complexes featuring two trans-coordinated NH,NH-stabilized carbene ligands.
• Subsequent reaction with phenyldivinylphosphine led to substitution of remaining phosphine ligands.
• An intramolecular hydroamination reaction successfully formed a macrocyclic complex, specifically [16]ane-P(2)C(NHC)(2) platinum(II) complex (1(PF(6))(2)).

Conclusions:

• Tetraphosphine platinum(II) complexes can be effectively converted into complexes bearing NH,NH-stabilized carbene ligands.
• The synthesized platinum-NHC complexes are amenable to further functionalization and macrocyclization.
• This study demonstrates a novel route to macrocyclic platinum complexes with potential applications in catalysis or materials science.