Au–Au Chemical Bonding in Nitronyl Nitroxide Gold(I) Derivatives

Au–Au Chemical Bonding in Nitronyl Nitroxide Gold(I) Derivatives Full article

Journal

Organometallics
ISSN: 1520-6041 , E-ISSN: 0276-7333

Output data

Year: 2022, Volume: 41, Number: 13, Pages: 1710-1720 Pages count : 11 DOI: 10.1021/acs.organomet.2c00200

Authors

Zayakin Igor A. ¹ , Korlyukov Alexander A. ² , Gorbunov Dmitry E. ^3,4 , Gritsan Nina P. ³ , Akyeva Anna Ya. ¹ , Syroeshkin Mikhail A. ¹ , Stass Dmitri V. ³ , Tretyakov Evgeny V. ¹ , Egorov Mikhail P. ¹

Affiliations

1	N.D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, Leninsky Avenue 47, Moscow 119991, Russian Federation
2	A.N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, Vavilova Street 28, Moscow 119991, Russian Federation
3	V.V. Voevodsky Institute of Chemical Kinetics and Combustion, Siberian Branch of Russian Academy of Sciences, 3 Institutskaya Street, Novosibirsk 630090, Russian Federation
4	A.V. Nikolaev Institute of Inorganic Chemistry, Siberian Branch of Russian Academy of Sciences, 3 Akad. Lavrentiev Avenue, Novosibirsk 630090, Russian Federation

Gold(I) derivatives of nitronyl nitroxide (NN) stabilized by complexation with phosphine ligands were designed to promote dimerization of the paramagnets in the solid state via Au–Au bonding. The complexes were successfully synthesized by the reaction of the corresponding phosphine [n-Bu3P or (4-FC6H4)3P], AuCl(THT), and NN–H under basic conditions in high yields. The gold(I) complexes were characterized by cyclic voltammetry, electron spin resonance, infrared, and UV/vis spectroscopy supported by quantum chemical calculations. Crystallographic analyses of the complexes showed that they possess Au–Au bonds (2.930 and 3.095 Å). The Au–Au bonding was confirmed by density functional theory calculations and quantum theory of “atoms in molecules” and natural bond orbital analyses, which made it possible to determine bond critical points (3, −1) and Au–Au bond orders (0.36 and 0.23) as well as to estimate the orbital contribution to the energy of Au–Au bonds (12.0 and 8.6 kcal/mol).

Zayakin I.A. , Korlyukov A.A. , Gorbunov D.E. , Gritsan N.P. , Akyeva A.Y. , Syroeshkin M.A. , Stass D.V. , Tretyakov E.V. , Egorov M.P.
Au–Au Chemical Bonding in Nitronyl Nitroxide Gold(I) Derivatives
Organometallics. 2022. V.41. N13. P.1710-1720. DOI: 10.1021/acs.organomet.2c00200 WOS Scopus OpenAlex

Web of science:	WOS:000818789600001
Scopus:	2-s2.0-85134464546
OpenAlex:	W4283378346

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