First Row Transition Metal(II) Thiocyanate Complexes, and Formation of 1-, 2-, and 3-Dimensional Extended Network Structures of M(NCS)2(Solvent)2 (M = Cr, Mn, Co) Composition
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- 作者：Endrit Shurdha ; Curtis E. Moore ; Arnold L. Rheingold ; Saul H. Lapidus ; Peter W. Stephens ; Atta M. Arif ; Joel S. Miller
- 刊名：Inorganic Chemistry
- 出版年：2013
- 出版时间：September 16, 2013
- 年：2013
- 卷：52
- 期：18
- 页码：10583-10594
- 全文大小：640K
- 年卷期：v.52,no.18(September 16, 2013)
- ISSN：1520-510X
文摘
The reaction of first row transition MII ions with KSCN in various solvents form tetrahedral (NMe4)2[MII(NCS)4] (M = Fe, Co), octahedral trans-MII(NCS)2(Sol)4 (M = Fe, V, Ni; Sol = MeCN, THF), and K4[MII(NCS)6] (M = V, Ni). The reaction of M(NCS)2(OCMe2)2 (M = Cr, Mn) in MeCN and [Co(NCMe)6](BF4)2 and KSCN in acetone and after diffusion of diethyl ether form M(NCS)2(Sol)2 that structurally differ as they form one-dimensional (1-D) (M = Co; Sol = THF), two-dimensional (2-D) (M = Mn; Sol = MeCN), and three-dimensional (3-D) (M = Cr; Sol = MeCN) extended structures. 1-D Co(NCS)2(THF)2 has trans-THFs, while the acetonitriles have a cis geometry for 2- and 3-D M(NCS)2(NCMe)2 (M = Cr, Mn). 2-D Mn(NCS)2(NCMe)2 is best described as MnII(渭N,N-NCS)(渭N,S-NCS)(NCMe)2 [= Mn2(渭N,N-NCS)2(渭N,S-NCS)2(NCMe)4] with the latter 渭N,S-NCS providing the 2-D connectivity. In addition, the reaction of Fe(NCS)2(OCMe2)2 and 7,7,8,8-tetracyanoquino-p-dimethane (TCNQ) forms 2-D structured FeII(NCS)2TCNQ. The magnetic behavior of 1-D Co(NCS)2(THF)2 can be modeled by a 1-D Fisher expression (H = 鈭?JSi路Sj) with g = 2.4 and J/kB = 0.68 K (0.47 cm鈥?) and exhibit weak ferromagnetic coupling. Cr(NCS)2(NCMe)2 and FeII(NCS)2TCNQ magnetically order as antiferromagnets with Tc鈥檚 of 37 and 29 K, respectively, while Mn(NCS)2(NCMe)2 exhibits strong antiferromagnetic coupling. M(NCS)2(THF)4 and K4[M(NCS)6] (M = V, Ni) are paramagnets with weak coupling between the octahedral metal centers.