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首页> 外文期刊>Chemistry: A European journal >Unprecedented Association of [Mo_6Br_7~iY~iBr_6~a]~_(3-) Cluster Units and [Mo~(III)Br_6]~(3_)Complexes:Synthesis,Crystal Structures,and Properties of the Double Salts Rb_3[Mo_6Br_7~iY~iBr_6~a](Rb_3[MoBr_6])_3 (Y =Se,Te)
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Unprecedented Association of [Mo_6Br_7~iY~iBr_6~a]~_(3-) Cluster Units and [Mo~(III)Br_6]~(3_)Complexes:Synthesis,Crystal Structures,and Properties of the Double Salts Rb_3[Mo_6Br_7~iY~iBr_6~a](Rb_3[MoBr_6])_3 (Y =Se,Te)

机译：[Mo_6Br_7〜iY〜iBr_6〜a] __（3-）簇单元与[Mo〜（III）Br_6]〜（3_）络合物的空前关联：复合盐的合成，晶体结构和性质Rb_3 [Mo_6Br_7〜 iY〜iBr_6〜a]（Rb_3 [MoBr_6]）_ 3（Y = Se，Te）

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The double salts Rb_3[Mo_6Br_7~iY~iBr_6~a](Rb_3[MoBr_6])_3 (Y =Se,Te)result from the partial dispro-portionation of the Mo_6Br_(12)octahe-dral-cluster-based bromide,in the pres-ence of corresponding chalcogenides and RbBr salt (crystal data:Rb_(12~-)[MoBr_6]_3[Mo_6Br_7~iTe~iBr_6~a] (1),Pm3m (No.221),a =12.1558(2)A,Z=l,R_1 =0.028;wR_2 =0.050;Rb_(12)[MoBr_6]_(3~-)[Mo_6Br_7~iSe~iBr_6~a] (2),Pm3m,a =12.144(3)A,Z=l,R1 =0.028;wR_2 =0.050).The structures of 1 and 2 are built up from [Mo~(III)Br_6]~(3-)complexes and [Mo_6Br_7~iY~iBr_6~a]~(3-) cluster units characterised by a andom distribution of seven bromine and one chalcogen li-gands on all the eight inner positions that face cap the Mo_6 clusters.Such a distribution implies a static orientation-al disorder of the [MO_6Br_7~iY~iBr_6~a]~(3-) units around the origin of the unit cell.Close-packed anionic layers based on[Mo~(III)Br_6]~(3-) complexes and [Mo_6Br_7~iY~iBr_6~a]~(3-) cluster units are stacked in the sequence ABC.This ar-rangement leads to very short Br~a-Br~a intercluster unit distances of 3.252 A,much lower than the sum of the van der Waals radii (3.70 A).The trivalent oxidation state of molybdenum in the Mo complexes and 24 valence electrons per Mo_6 cluster have been confirmed by magnetic susceptibility measure-ments.Salts 1 and 2 constitute the first examples of structurally characterised bromides containing discrete [Mo~(III)Br_6]~(3-)complexes obtained by means of solid-state synthesis.
机译：复盐Rb_3 [Mo_6Br_7〜iY〜iBr_6〜a]（Rb_3 [MoBr_6]）_ 3（Y = Se，Te）是由于Mo_6Br_（12）八面体-对苯二酚基溴化物的部分歧化所致存在相应的硫属化物和RbBr盐（晶体数据：Rb_（12〜-）[MoBr_6] _3 [Mo_6Br_7〜iTe〜iBr_6〜a]（1），Pm3m（No.221），a = 12.1558（2） A，Z = l，R_1 = 0.028; wR_2 = 0.050; Rb_（12）[MoBr_6] _（3〜-）[Mo_6Br_7〜iSe〜iBr_6〜a]（2），Pm3m，a = 12.144（3）A， Z = 1，R1 = 0.028; wR_2 = 0.050）.1和2的结构由[Mo〜（III）Br_6]〜（3-）配合物和[Mo_6Br_7〜iY〜iBr_6〜a]〜（3 -）团簇单元，特征是在面对Mo_6团簇的所有八个内部位置上有七个溴和一个硫族元素配体的无规分布。这种分布意味着[MO_6Br_7〜iY〜iBr_6〜 a]〜（3-）单位围绕着晶胞的起点。基于[Mo〜（III）Br_6]〜（3-）配合物和[Mo_6Br_7〜iY〜iBr_6〜a]〜（3 -）群集单元按顺序ABC堆叠。到极短的Br〜a-Br〜a簇间单位距离为3.252 A，远低于范德华半径的总和（3.70 A）。Mo络合物中钼的三价氧化态和每Mo_6含24个价电子盐1和2构成了结构表征的溴化物的第一个实例，该溴化物包含通过固态合成获得的离散[Mo〜（III）Br_6]〜（3-）配合物。

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