Heterobimetallic Lantern Complexes That Couple Antiferromagnetically through Noncovalent Pt路路路Pt Interactions

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• 作者：Frederick G. Baddour ; Stephanie R. Fiedler ; Matthew P. Shores ; James A. Golen ; Arnold L. Rheingold ; Linda H. Doerrer
• 刊名：Inorganic Chemistry
• 出版年：2013
• 出版时间：May 6, 2013
• 年：2013
• 卷：52
• 期：9
• 页码：4926-4933
• 全文大小：332K
• 年卷期：v.52,no.9(May 6, 2013)
• ISSN：1520-510X

文摘

A series of Pt-based heterobimetallic lantern complexes of the form [PtM(SAc)₄(OH₂)] (M = Co, 1; Ni, 2; Zn, 3) were prepared using a facile, single-step procedure. These hydrated species were reacted with 3-nitropyridine (3-NO₂py) to prepare three additional lantern complexes, [PtM(SAc)₄(3-NO₂py)] (M = Co, 4; Ni, 5; Zn, 6), or alternatively dried in vacuo to the dehydrated species [PtM(SAc)₄] (M = Co, 7; Ni, 8; Zn, 9). The Co- and Ni-containing species exhibit Pt鈥擬 bonding in solution and the solid state. In the structurally characterized compounds 1鈥?b>6, the lantern units form dimers in the solid state via a short Pt路路路Pt metallophilic interaction. Antiferromagnetic coupling between 3d metal ions in the solid state through noncovalent metallophilic interactions was observed for all the paramagnetic lantern complexes prepared, with J-coupling values of 鈭?2.7 cmp>鈥?p> (1), 鈭?0.8 cmp>鈥?p> (2), 鈭?.0 cmp>鈥?p> (4), and 鈭?2.6 cmp>鈥?p> (5). The Zn complexes 3 and 6 also form solid-state dimers, indicating that the formation of short Pt路路路Pt interactions in these complexes is not predicated on the presence of a paramagnetic 3d metal ion. These contacts and the resultant antiferromagnetic coupling are also not unique to heterobimetallic lantern complexes with axially coordinated H₂O or the previously reported thiobenzoate supporting ligand.