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Which Is the Stronger Nucleophile, Platinum or Nitrogen in Rollover Cycloplatinated(II) Complexes?

Fatemeh Niroomand Hosseini, S Masoud Nabavizadeh, Mahdi M Abu-Omar

Inorg Chem. 2017 Dec 4;56(23):14706-14713.

PMID: 29154540

Abstract:

The rollover cyclometalated platinum(II) complexes [PtMe(2,X'-bpy-H)(PPh3)], (X = 2, 1a; X = 3, 1b; and X = 4, 1c) containing two potential nucleophilic centers have been investigated to elucidate which center is the stronger nucleophile toward methyl iodide. On the basis of DFT calculations, complexes 1b and 1c are predicted reacting with MeI through the free nitrogen donor to form N-methylated platinum(II) complexes, while complex 1a reacts through oxidative addition on platinum to give a platinum(IV) complex, which is in agreement with experimental findings. The reasons for this difference in selectivity for complexes 1a-1c are discussed based on the energy barrier needed for N-methylation versus oxidative addition reactions.

Chemicals Related in the Paper:

Catalog Number Product Name Structure CAS Number Price
AP7790398 Platinum(II) iodide Platinum(II) iodide 7790-39-8 Price
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