## Abstract

The stretching frequency, ν(Cu-O), of the [CuOH]^{2+} core in the complexes LCuOH (L = N,N′-bis(2,6-diisopropyl-4-R-phenyl)pyridine-2,6-dicarboxamide, R = H or NO_{2}, or N,N′-bis(2,6-diisopropylphenyl)-1-methylpiperidine-2,6-dicarboxamide) was determined to be ∼630 cm^{-1} by resonance Raman spectroscopy and verified by isotopic labeling. In efforts to use Badger's rule to estimate the bond distance corresponding to ν(Cu-O), a modified version of the rule was developed through use of stretching frequencies normalized by dividing by the appropriate reduced masses. The modified version was found to yield excellent fits of normalized frequencies to bond distances for >250 data points from theory and experiment for a variety of M-X and X-X bond distances in the range ∼1.1-2.2 Å (root mean squared errors for the predicted bond distances of 0.03 Å). Using the resulting general equation, the Cu-O bond distance was predicted to be ∼1.80 Å for the reactive [CuOH]^{2+} core. Limitations of the equation and its use in predictions of distances in a variety of moieties for which structural information is not available were explored.

Original language | English (US) |
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Pages (from-to) | 4477-4485 |

Number of pages | 9 |

Journal | Journal of the American Chemical Society |

Volume | 139 |

Issue number | 12 |

DOIs | |

State | Published - Mar 29 2017 |

### Bibliographical note

Funding Information:We thank the National Institutes of Health (R37GM47365 to W.B.T.) for financial support of this research. The authors thank Benjamin D. Neisen and Dr. Victor G. Young, Jr. for assistance with X-ray crystallography and Dr. Patrick L. Holland for sharing O-O and N-N Badger's rule data. This work was carried out in part using computing resources at the University of Minnesota Supercomputing Institute.