Department of Chemistry, Northwestern University, Evanston, Illinois, 60208-3113, United States.
Inorg Chem. 2011 Oct 3;50(19):9688-95. doi: 10.1021/ic201493w. Epub 2011 Sep 1.
Black crystals of Np(PS(4)), Np(P(2)S(6))(2), K(11)Np(7)(PS(4))(13), and Rb(11)Np(7)(PS(4))(13) have been synthesized by the reactions of Np, P(2)S(5), and S at 1173 and 973 K; Np, K(2)S, P, and S at 773 K; and Np, Rb(2)S(3), P, and S at 823 K, respectively. The structures of these compounds have been characterized by single-crystal X-ray diffraction methods. Np(PS(4)) adopts a three-dimensional structure with Np atoms coordinated to eight S atoms from four bidentate PS(4)(3-) ligands in a distorted square antiprismatic arrangement. Np(PS(4)) is isostructural to Ln(PS(4)) (Ln = La-Nd, Sm, Gd-Er). The structure of Np(P(2)S(6))(2) is constructed from three interpenetrating diamond-type frameworks with Np atoms coordinated to eight S atoms from four bidentate P(2)S(6)(2-) ligands in a distorted square antiprismatic geometry. The centrosymmetric P(2)S(6)(2-) anion comprises two PS(2) groups connected by two bridging S centers. Np(P(2)S(6))(2) is isostructural to U(P(2)S(6))(2). A(11)Np(7)(PS(4))(13) (A = K, Rb) adopts a three-dimensional channel structure built from interlocking Np(7)(PS(4))(13)-screw helices with A cations residing in the channels. The structure of A(11)Np(7)(PS(4))(13) includes four crystallographically independent Np atoms. Three are connected to eight S atoms in bicapped trigonal prisms. The other Np atom is connected to nine S atoms in a tricapped trigonal prism. A(11)Np(7)(PS(4))(13) is isostructural to A(11)U(7)(PS(4))(13). From Np-S bond distances and charge-balance, we infer that Np is trivalent in Np(PS(4)) and tetravalent in Np(P(2)S(6))(2) and A(11)Np(7)(PS(4))(13). Np exhibits a behavior intermediate between U and Pu in its thiophosphate chemistry.
已通过 Np、P2S5 和 S 在 1173 和 973 K、Np、K2S、P 和 S 在 773 K 以及 Np、Rb2S3、P 和 S 在 823 K 下的反应分别合成了 Np(PS4)、Np(P2S6)2、K11Np7(PS4)13 和 Rb11Np7(PS4)13 的黑色晶体。这些化合物的结构通过单晶 X 射线衍射方法进行了表征。Np(PS4)采用三维结构，其中 Np 原子与来自四个双齿 PS43-配体的八个 S 原子配位，呈扭曲的四方反棱柱体排列。Np(PS4)与 Ln(PS4)（Ln = La-Nd、Sm、Gd-Er）结构相同。Np(P2S6)2 的结构由三个互穿的金刚石型骨架组成，其中 Np 原子与来自四个双齿 P2S62-配体的八个 S 原子配位，呈扭曲的四方反棱柱体几何形状。中心对称的 P2S62-阴离子由两个通过两个桥接 S 中心连接的 PS2 基团组成。Np(P2S6)2 与 U(P2S6)2 结构相同。A11Np7(PS4)13（A = K、Rb）采用由互锁Np7(PS4)13-螺旋构成的三维通道结构，其中 A 阳离子位于通道中。A11Np7(PS4)13 的结构包含四个结晶学上独立的 Np 原子。其中三个与八个 S 原子连接形成双帽三角棱柱，另一个与九个 S 原子连接形成三帽三角棱柱。A11Np7(PS4)13 与 A11U7(PS4)13 结构相同。根据 Np-S 键距离和电荷平衡，我们推断 Np 在 Np(PS4)中为三价，在 Np(P2S6)2 和 A11Np7(PS4)13 中为四价。Np 在其硫代磷酸盐化学中表现出介于 U 和 Pu 之间的行为。
