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Keywords:

  • density functional calculations;
  • metallophthalocyanines;
  • N ligands;
  • ruthenium;
  • structure elucidation

Abstract

A “metal–ketimine+ArI(OR)2” approach has been developed for preparing metal–ketimido complexes, and ketimido ligands are found to stabilize high-valent metallophthalocyanine (M[BOND]Pc) complexes such as ruthenium(IV) phthalocyanines. Treatment of bis(ketimine) ruthenium(II) phthalocyanines [RuII(Pc)(HN[DOUBLE BOND]CPh2)2] (1a) and [RuII(Pc)(HNQu)2] (1b; HNQu=N-phenyl-1,4-benzoquinonediimine) with PhI(OAc)2 affords bis(ketimido) ruthenium(IV) phthalocyanines [RuIV(Pc)(N[DOUBLE BOND]CPh2)2] (2a) and [RuIV(Pc)(NQu)2] (2b), respectively. X-ray crystal structures of 1b and [RuII(Pc)(PhN[DOUBLE BOND]CHPh)2] (1c) show Ru[BOND]N(ketimine) distances of 2.075(4) and 2.115(3) Å, respectively. Complexes 2a,2b readily revert to 1a,1b upon treatment with phenols. 1H NMR spectroscopy reveals that 2a,2b are diamagnetic and 2b exists as two isomers, consistent with a proposed eclipsed orientation of the ketimido ligands in these ruthenium(IV) complexes. The reaction of 1a,1b with PhI(OAc)2 to afford 2a,2b suggests the utility of ArI(OR)2 as an oxidative deprotonation agent for the generation of high-valent metal complexes featuring M[BOND]N bonds with multiple bonding characters. DFT and time-dependent (TD)-DFT calculations have been performed on the electronic structures and the UV/Vis absorption spectra of 1b and 2b, which provide support for the diamagnetic nature of 2b and reveal a significant barrier for rotation of the ketimido group about the Ru[BOND]N(ketimido) bond.

Featured Compounds

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  1. 1 - 7
Compound 1a
Molecular Weight:976.06
Molecular Formula:C58H38N10Ru
InChIKey:SIACBOHVCVPIMF-UHFFFAOYSA-N
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Compound 1b
Molecular Weight:978.04
Molecular Formula:C56H36N12Ru
InChIKey:FWLAJIJFVHJELS-HTFOKDTBSA-N
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Compound 2a
Molecular Weight:974.04
Molecular Formula:C58H36N10Ru
InChIKey:DSHJHHPRSOGXST-UHFFFAOYSA-N
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Compound 2b
Molecular Weight:976.02
Molecular Formula:C56H34N12Ru
InChIKey:JSPUUJDORYMXEF-UHFFFAOYSA-N
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Compound 1c
Molecular Weight:976.06
Molecular Formula:C58H38N10Ru
InChIKey:RLERSVVEXJQBQP-SXCDESCTSA-N
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Compound 1
Molecular Weight:Not Available
Molecular Formula:Not Available
InChIKey:Not Available
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Compound 2
Molecular Weight:Not Available
Molecular Formula:Not Available
InChIKey:Not Available
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