Study of a cyclometalated complex of ruthenium by 400-MHz two-dimensional proton NMR

Abstract

demonstrated that chelating thiolates can support an oligomeric array in which the metal atoms, although possessing essentially the same immediate coordination geometry, are rendered inequivalent by the chelate arrangement. This consideration should not be ignored in any interpretation of the spectroscopic in-equivalence30 of the metal centers of the metallothioneins and related proteins.Acknowledgment. We thank S. Bristow for his considerable assistance and expertise in the recording and assignment of 13C NMR spectra and the SERC for financial support (to J.R.N. and I.L.A.). 94957-37-6. Supplementary Material Available: Listings of all the calculated atomic coordinates, anisotropic thermal parameters, isotropic thermal parameters for hydrogen atoms, remaining bond lengths and bond angles, and |F0| and |FC| values (40 pages). Ordering information is given on any current masthead page.

Synthesis, Crystal Structure, and Second‐Order Nonlinear Optical Properties of Ruthenium(II) Complexes with Substituted Bipyridine and Phenylpyridine Ligands

“…Characteristic peaks of cyclometalated compounds were observed in the NMR spectra of [Ru(bpy) 2 -(L 1 )][PF 6 ] and the peaks of the spectra were fully assigned. [14,23,24] …”

A new cycloruthenated complex: Synthesis, characterization and colorimetric detection of bisulphite in water

“…S1. Upon cyclometallation, there were significant upfield shifts for all aromatic cyclometallating ligand proton signals because cyclometallation resulted in a significant increase in electron density on the ligand [39,40]. For example, the singlet assigned to hydrogen signal of aldehyde shifted from d 10.09 to 9.72 ppm.…”

Recognition of DNA Base Pair Mismatches by a Cyclometalated Rh(III) Intercalator

“…Two new cyclometalated Rh(III) complexes, [Rh(ppy) 2 phi]Cl and [Rh(ppy) 2 -chrysi]Cl, have been prepared (Figure 1). [Rh(ppy) 2 phi]Cl was synthesized via the addition of commercially available 9,10-diaminophenanthrene to the dichlorodimer, [Rh(ppy) 2 Cl] 2 , in DMF in the presence of atmospheric oxygen. The product was purified by crystallization from a concentrated 1:1 dichloromethane/ethyl acetate solution with an overall yield of 30%.…”

“…The UV-visible spectra of [Rh(bpy) 2 Figure 2b. The spectrum of [Rh(bpy) 2 chrysi]Cl 3 , which has a pK a of 5.2, shows two LMCT transitions at 399 and 462 nm under acidic conditions.…”

“…1 The changes in such properties observed upon the replacement of a typical N,Ndonor ligand such as 2,2′-bipyridine with its carbocylic structural analogue, 2-phenylpyridine (ppy), have been of particular interest. 2 Replacing 2,2′-bipyridine with 2-phenylpyridine, a C,N-donor due to its σ-donor/π-acceptor properties, results in higher energy d-d excited states and increasingly lower energy metal-to-ligand charge transfer states as well as a decrease in overall charge with increasing number of M-C σ-bonds. 1,3 This laboratory has focused on the design of metallointercalators containing functionalized polypyridyl ligands to achieve site-specific DNA recognition.…”