cross-[B20H18]2- in Copper(I), Silver(I), and Cadmium(II) Complexation: Formation of [a2-B20H18]4- and [B20H16]4- Tetraanions.

Authors

Varvara V Avdeeva, Albina E Gerusova, Alexey S Kubasov, Aleksei V Golubev, Ilya N Klyukin, Nikolay T Kuznetsov

Published in

Inorganic chemistry. Volume 65. Issue 41. Pages 24097-24102. Oct 19, 2026.

Abstract

The cross-[B20H18]2- anion, a synthetic challenge for decades, is introduced into coordination chemistry for the first time. Contrary to the well-behaved trans and iso isomers, the cross-[B20H18]2- exhibits unprecedented reactivity toward d10 metal ions (Cu+, Ag+, Cd2+), undergoing spontaneous reduction under ambient conditions in acetonitrile affording the reduced a2-[B20H18]4- anion in copper(I) and cadmium(II) complexes, and─remarkably─the previously unknown [B20H16]4- species in the silver(I) system. The resulting complexes, [Ag4(Ph3P)4[B20H16]] (1), (Et3NH)2[Cu2(PPh3)2[a2B20H18]] (2), and [Ph3PCH2Naph][Cd2(phen)2(CF3COO)[a2-B20H18]] (3), were characterized by single-crystal X-ray diffraction, 11B NMR (only for 2), and IR spectroscopy. Density functional theory calculations at the B97MD4/def2-TZVPP level confirm a2-[B20H18]4- as the thermodynamically most stable reduced form, with the strongest intercage B-B bond. This work not only establishes the cross isomer as a distinct entry point to boron cluster chemistry but also provides a remarkably simple, one-pot route to reduced boron-rich ligands.

PMID:
42895401
Bibliographic data and abstract were imported from PubMed on 19 Oct 2026.

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