Comparison of {O,S}- vs {N,S}-donor ligands in PtNi heterobimetallic lantern complexes

被引：4
|
作者：
Beach, Stephanie A. [1 ]
Rheingold, Arnold L. [2 ]
Doerrer, Linda H. [1 ]
机构：
[1] Boston Univ, Dept Chem, 590 Commonwealth Ave, Boston, MA 02215 USA
[2] Univ Calif San Diego, Dept Chem & Biochem, 9500 Gilman Dr, La Jolla, CA 92093 USA
来源：
POLYHEDRON | 2021年 / 208卷
基金：
美国国家科学基金会;
关键词：
Platinum; Nickel; Lantern; Paddlewheel; Mercaptopyridine thiocarboxylate; CENTER-DOT-PT; BUILDING-BLOCK; MOLECULES; PYRIDINE-2-THIOLATE; DIMOLYBDENUM(II); SUSCEPTIBILITY; PLATINUM(II); OXIDATION; RHODIUM;
D O I：
10.1016/j.poly.2021.115403
中图分类号：
O61 [无机化学];
学科分类号：
070301 ; 081704 ;
摘要：
A pair of thiocarboxylate lantern complexes, [PtNi(SAc)(4)(L)] (L = pyCN (2), HpipCN (3)) and three new {N,S} chelated mercaptopyridine lantern complexes [PtNi(mpyS)(4)(L)] (L = H2O (4), MeCN (5), pyCN (6)) have been synthesized and characterized by SCXRD, H-1 NMR and UV-vis spectroscopies, as well as elemental analysis and RT solution magnetization. A detailed structural comparison was made of the {O,S} and {N, S} donor systems that demonstrates that the stronger field mercaptopyridine ligand decreases the Pt (donor) - M (acceptor) character within the lantern, reducing the Pt(II) Lewis acidity and therefore preventing the formation of intermolecular interactions in Ni(II) complexes 4-6. An unexpected pentameric species [Pt(PtNi(mpyS)(4)(Cl))(2)] (7) was also formed, albeit in very low quantities, that showed the importance of the choice of Ni(II) starting material. Additionally, the development of an improved air- and water-stable synthesis for the formation of the homo-leptic, Pt-2(PYS)(4)], is reported.
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页数：13
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