Publication detail

Control of Complex Formation through Peripheral Substituents in Click-Tripodal Ligands: Structural Diversity in Homo-and Heterodinuclear Cobalt-Azido Complexes

Sommer, MG. Marx, R. Schweinfurth, D. Rechkemmer, Y. Neugebauer, P. van der Meer, M. Meyer, F. van Slageren, J. Sarkar, B.

Original Title

Control of Complex Formation through Peripheral Substituents in Click-Tripodal Ligands: Structural Diversity in Homo-and Heterodinuclear Cobalt-Azido Complexes

Type

journal article in Web of Science

Language

English

Original Abstract

The azide anion is widely used as a ligand in coordination chemistry. Despite its ubiquitous presence, controlled synthesis of azido complexes remains a challenging task. Making use of click-derived tripodal ligands, we present here various coordination motifs of the azido ligands, the formation of which appears to be controlled by the peripheral substituents on the tripodal ligands with otherwise identical structure of the coordination moieties. Thus, the flexible benzyl substituents on the tripodal ligand TBTA led to the formation of the first example of an unsupported and solely ptixazido-bridged dicobalt(II) complex. The more rigid phenyl substituents on the TPTA ligand deliver an unsupported and solely mu(1,3),-azido-bridged dicobalt(II) complex. Bulky diisopropylphenyl substituents on the TDTA ligand deliver a doubly mu(1,1),-azido-bridged dicobalt(II) complex. Intriguingly, the mononuclear copper(II) complex [Cu(TBTA)N-3](+) is an excellent synthon for generating mixed dinuclear complexes of the form [(TBTA)Co(mu(1,1)-N-3)Cu(TBTA)](3+) or [(TBTA)Cu(mu(1,1)-N-3)Cu(TPTA)](3+), both of which contain a single unsupported mu(1,1)-N-3 as a bridge. To the best of our knowledge, these are also the first examples of mixed dinuclear complexes with a monoazido bridge. All complexes were crystallographically characterized, and selected examples were probed-via magnetometry and high-field EPR spectroscopy to elucidate the electronic structures of these complexes and the nature of magnetic coupling in the various azido-bridged complexes. These results thus prove the power of click-tripodal ligands in generating hitherto unknown chemical structures and properties.

Keywords

TETRANUCLEAR NICKEL(II) COMPLEXES; TRANSITION-METAL-COMPLEXES; MAGNETIC-PROPERTIES; GROUND-STATE; CRYSTAL-STRUCTURE; SPIN-CROSSOVER; 1.3-DIPOLARE CYCLOADDITIONEN; ELECTRONIC-STRUCTURES; BINUCLEAR COMPLEXES; RUTHENIUM COMPLEXES

Authors

Sommer, MG.; Marx, R.; Schweinfurth, D. ; Rechkemmer, Y.; Neugebauer, P.; van der Meer, M.; Meyer, F. ; van Slageren, J.; Sarkar, B.

Released

2. 1. 2017

ISBN

0020-1669

Periodical

Inorganic Chemistry

Year of study

56

Number

1

State

United States of America

Pages from

402

Pages to

413

Pages count

12

BibTex

@article{BUT146430,
  author="Sommer, MG. and Marx, R. and Schweinfurth, D. and Rechkemmer, Y. and Neugebauer, P. and van der Meer, M. and Meyer, F. and van Slageren, J. and Sarkar, B.",
  title="Control of Complex Formation through Peripheral Substituents in Click-Tripodal Ligands: Structural Diversity in Homo-and Heterodinuclear Cobalt-Azido Complexes",
  journal="Inorganic Chemistry",
  year="2017",
  volume="56",
  number="1",
  pages="402--413",
  doi="10.1021/acs.inorgchem.6b02330",
  issn="0020-1669"
}