Conformational and electronic variability of N,N’,O-ligand documented on its coordination to main group halides

Abstract

The coordination chemistry of non-symmetric ligand L (L = 2-(C(Me)[double bond, length as m-dash]N(C6H3-2,6-iPr2))-6-((iPrO)2P[double bond, length as m-dash]O)C5H3N) is with a focus on its ability to adapt its denticity to accommodate different main-group elements within a potentially tridentate ‘pocket’ defined by its phosphonate P[double bond, length as m-dash]O and imine C[double bond, length as m-dash]N groups together with the pyridine-nitrogen atom. For this purpose, chlorides of groups 13, 14, and 16 were selected, namely InCl3, GeCl2, Ph3SnCl, Ph2SnCl2, SeCl4 and TeCl4. The reaction of L with GeCl2 and InCl3 produced [GeCl(L)][GeCl3] (2) and [InCl3(L)] (5), respectively. In both compounds, L coordinates to the central metal through all its donor atoms with a κ3-N,N,O-coordination mode. On the contrary, L coordinates Ph3SnCl and Ph2SnCl2 through only the phosphonate P[double bond, length as m-dash]O group, resulting in κ1-O-coordinated [Ph3SnCl(L)] (3) and [Ph2SnCl2(L)] (4). The diverse chelating ability of L was found in the reaction with TeCl4 and SeCl4 yielding 2-(C(CH[double bond, length as m-dash]SeCl2)[double bond, length as m-dash]N(Dipp))-6-((iPrO)2P[double bond, length as m-dash]O)C5H3N (6) and 2-(C(CH2TeCl3)[double bond, length as m-dash]N(Dipp))-6-((iPrO)2P[double bond, length as m-dash]O)C5H3N (7) as a result of a C–H bond activation in the Me group of the C(Me)[double bond, length as m-dash]N fragment. Due to the presence of the M–Cl bond, all compounds 2–7 were subjected to reduction reactions with the aim of synthesising low-valent derivatives. However, only the reduction of 2 with K or KC8 led to the successful isolation of a product, [Ge(L)] (8). Finally, theoretical studies were carried out to better understand the formation of 6 and 7 as well as the electronic properties of 8.

Graphical abstract: Conformational and electronic variability of N,N’,O-ligand documented on its coordination to main group halides

Supplementary files

Article information

Article type
Paper
Submitted
16 May 2025
Accepted
08 Jul 2025
First published
08 Jul 2025
This article is Open Access
Creative Commons BY license

Dalton Trans., 2025, Advance Article

Conformational and electronic variability of N,N’,O-ligand documented on its coordination to main group halides

Y. Milasheuskaya, Z. Růžičková, A. Růžička, Š. Podzimek, R. Jambor and M. Novák, Dalton Trans., 2025, Advance Article , DOI: 10.1039/D5DT01155H

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