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Remarkable coordination variability of the P,C,P-pincer ligand in organotin(iv) compounds - a promising outlook for other p-block elements
Authors: Chlebík Richard | Kertesz Erik | Erben Milan | Růžička Aleš | Jambor Roman | Benko Zoltan | Dostál Libor
Year: 2025
Type of publication: článek v odborném periodiku
Name of source: Dalton Transactions
Publisher name: Royal Society of Chemistry
Place: Cambridge
Page from-to: 15093-15106
Titles:
Language Name Abstract Keywords
cze Pozoruhovná koordinační flexibility P,C,P-pincer ligandů v chemii organocíničitých sloučenin - slibná zpráva pro ostatní p-prvky Je popsáno první použití PCP pincerových ligandů v chemii organocíničitých sloučenin, které poskytlo bohatou paletu koordinačních módů. Struktura sloučenin byla studována pomocí NMR, difrakční analýzy i teoreticky. PCP pincer komplexy; kationty; cín; strukturální studie
eng Remarkable coordination variability of the P,C,P-pincer ligand in organotin(iv) compounds - a promising outlook for other p-block elements The coordination properties of the P,C,P-pincer ligand (Ar = 2,6-(tBu2PO)2C6H3) with organotin(iv) compounds were examined. For this purpose, a set of neutral compounds including ArSnPh2Cl (1), ArSnPhCl2 (2) and ArSnCl3 (3), ArSnBu3 (4) and the cations [ArSnPh2][BArF] (1+[BArF]-), [ArSnPhCl][BArF] (2+[BArF]-), [ArSnCl2][BArF] and (3+[BArF]-) ([BArF] = [3,5-(CF3)2C6H3]4B) were prepared and characterized by multinuclear NMR spectroscopy and single-crystal (sc) X-ray diffraction analysis (2, 3, 1+[BArF]- and 3+[BArF]-). This study revealed different types of ligand coordination, i.e. no P -> Sn intramolecular interaction in 1 and 2, while one P atom is coordinated in 3 and both P atoms in tin cations 1+, 2+ and 3+. To further elucidate the strength of these P -> Sn dative bonds, all compounds were reacted with [BH3(SMe2)] to prove whether it coordinates toward pendant P atoms or even de-coordinates those P atoms already connected to the tin atom. Thus, in 1, 2, and 4, both P atoms formed complexes with the borane, while in 3 only one phosphorus reacted with BH3, because the second remained bonded to the tin atom. Finally, even in the cation 1+ one of the P atoms could be blocked by borane leaving the tin atom four-coordinated, while it was not possible for 2+ and 3+. DFT calculations were used to gain a deeper insight into the P -> Sn bonding interaction in the studied compounds. PCP pincer complexes; cations; tin; structural study

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