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How can a positively charged nitrenium ligand bind a positively charged metal? A 2013 Chemical Science study reported rhodium and platinum complexes in which the two cationic centers remain bonded. The Royal Society of Chemistry’s 10 January 2014 summary attributes that kinetic persistence to the ligand’s shape—not to a general attraction between like charges.
What makes these complexes unusual?
Like charges repel, so a bond between a cationic ligand and a cationic metal may seem counterintuitive. But repulsion is not the only interaction at work: the RSC summary explains that bonding can also involve attraction between the nuclei of one cation and the electrons of the other.
The reported compounds pair cationic nitrenium ligands with cationic rhodium or platinum centers. The result is a specific case of cation–cation bonding, not evidence that positively charged species generally attract or form stable bonds.
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The ligand has a pincer-type structure: a central nitrenium moiety flanked by two phosphine arms. The RSC describes these ligands as nitrogen analogues of N-heterocyclic carbenes. The arms coordinate the metal and keep it positioned near the central nitrogen.
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According to the RSC account, computational investigations indicate that this coordination geometry creates a kinetic barrier to breaking the nitrogen–metal bond. In other words, the structure makes dissociation difficult enough for the complexes to persist. That explanation concerns kinetic stability; the summary does not claim the compounds are thermodynamically stable.
What did the study establish—and what did it not?
The researchers prepared rhodium and platinum forms of the complexes, as summarized by the Royal Society of Chemistry. The account does not provide quantitative measurements or comparative performance data, so it does not support a numerical assessment of bond strength or stability against other complexes.
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The summary suggests that the compounds could offer opportunities for organic transformations, but it does not identify a demonstrated catalytic reaction. The result is therefore a report of unusual, kinetically persistent metal complexes and a possible research direction—not proof of a practical or commercial catalyst.
Which paper is behind the report?
The RSC summary covers “Cation-Cation Bonding in Nitrenium Metal Complexes,” by Mark Gandelman, Yuri Tulchinsky, Prasenjit Saha, Sebastian Kozuch, Mark Botoshansky and Linda Shimon. The paper appeared in Chemical Science in 2013; its DOI is 10.1039/C3SC53083C. The Royal Society of Chemistry published its blog summary, “Nitrenium hugs stabilise positively rare complexes,” on 10 January 2014: RSC summary.
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