TY - JOUR
T1 - Structural Investigation of Magnesium Complexes Supported by a Thiopyridyl Scorpionate Ligand
AU - Stevens, Matthew P.
AU - Spray, Emily
AU - Vitorica-Yrezabal, Iñigo J.
AU - Singh, Kuldip
AU - Timmermann, Vanessa M.
AU - Sotorríos, Lia
AU - Ortu, Fabrizio
N1 - Funding Information:
This research was funded by the Royal Society (RGS\R2\202097) and Engineering and Physical Sciences Research Council (EP/W00691X/1, EP/T019876/1). X-ray diffraction at Leicester was also supported by the Engineering and Physical Sciences Research Council (EP/V034766/1).
Publisher Copyright:
© 2022 by the authors.
PY - 2022/7/18
Y1 - 2022/7/18
N2 - Herein, we report the synthesis of a series of heteroleptic magnesium complexes stabilized with the scorpionate ligand tris(2-pyridylthio)methanide (Tptm). The compounds of the general formula [Mg(Tptm)(X)] (1-X; X = Cl, Br, I) were obtained via protonolysis reaction between the proligand and selected Grignard reagents. Attempts to isolate the potassium derivative K(Tptm) lead to decomposition of Tptm and formation of the alkene (C5H4N-S)2C=C(C5H4N-S)2, and this degradation was also modelled using DFT methods. Compound 1-I was treated with K(CH2Ph), affording the degradation product [Mg(Bptm)2] (2; Bptm = {CH(S-C5NH3)2}−). We analyzed and quantified the steric properties of the Tptm ligand using the structural information of the compounds obtained in this study paired with buried volume calculations, also adding the structural data of HTptm and its CF3-substituted congener (HTptmCF3). These studies highlight the highly flexible nature of this ligand scaffold and its ability to stabilize various coordination motifs and geometries, which is a highly desirable feature in the design of novel organometallic reagents and catalysts.
AB - Herein, we report the synthesis of a series of heteroleptic magnesium complexes stabilized with the scorpionate ligand tris(2-pyridylthio)methanide (Tptm). The compounds of the general formula [Mg(Tptm)(X)] (1-X; X = Cl, Br, I) were obtained via protonolysis reaction between the proligand and selected Grignard reagents. Attempts to isolate the potassium derivative K(Tptm) lead to decomposition of Tptm and formation of the alkene (C5H4N-S)2C=C(C5H4N-S)2, and this degradation was also modelled using DFT methods. Compound 1-I was treated with K(CH2Ph), affording the degradation product [Mg(Bptm)2] (2; Bptm = {CH(S-C5NH3)2}−). We analyzed and quantified the steric properties of the Tptm ligand using the structural information of the compounds obtained in this study paired with buried volume calculations, also adding the structural data of HTptm and its CF3-substituted congener (HTptmCF3). These studies highlight the highly flexible nature of this ligand scaffold and its ability to stabilize various coordination motifs and geometries, which is a highly desirable feature in the design of novel organometallic reagents and catalysts.
KW - DFT
KW - alkaline earth
KW - buried volume calculations
KW - inorganic
KW - ligand design
KW - organometallic chemistry
KW - scorpionate
UR - http://www.scopus.com/inward/record.url?scp=85135103641&partnerID=8YFLogxK
U2 - 10.3390/molecules27144564
DO - 10.3390/molecules27144564
M3 - Article
C2 - 35889437
SN - 1420-3049
VL - 27
JO - Molecules
JF - Molecules
IS - 14
M1 - 4564
ER -