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四烷基铵金属异硫氰酸盐盐的合成、结构和光散射性质。

Synthesis, structure and light scattering properties of tetraalkylammonium metal isothiocyanate salts.

机构信息

Department of Chemistry, Simon Fraser University, 8888 University Drive, Burnaby, B.C., V5A 1S6, Canada.

出版信息

Dalton Trans. 2013 Nov 14;42(42):14982-91. doi: 10.1039/c3dt50974e. Epub 2013 Aug 12.

Abstract

A series of ammonium and tetraalkylammonium metal isothiocyanate salts of the type Q(y)[M(NCS)x] (M = Cr(III), x = 6, y = 3, Q = NH4(+), Me4N(+), Et4N(+), n-Bu4N(+); M = Mn(II), x = 6, y = 4, Q = Me4N(+); M = Mn(II), x = 5, y = 3, Q = Et4N(+); M = Fe(III), x = 6, y = 3, Q = Me4N(+), Et4N(+), n-Bu4N(+); M = Co(II), x = 4, y = 2, Q = n-Bu4N(+); M = Eu(III), Gd(III), Dy(III), x = 6, y = 3, Q = Bu4N(+)) has been synthesized and structurally characterized. The octahedral Cr(III) salts are isostructural to previously and newly reported Fe(III) salts. The Ln(III)-containing anions are also octahedral. For Mn(II), although the Me4N(+) salt is octahedral, the Et4N(+) salt Mn(NCS)5 possesses a distorted trigonal bipyramidal geometry. For (Et4N)3[Fe(NCS)6] and (n-Bu4N)3[Fe(NCS)6], a solid-state size-dependent change in colour from red to green was observed and was attributed to a light scattering phenomenon in the crystalline samples.

摘要

已合成并结构表征了一系列类型为 Q(y)[M(NCS)x] 的铵和四烷基铵金属异硫氰酸盐盐(M = Cr(III),x = 6,y = 3,Q = NH4(+),Me4N(+),Et4N(+),n-Bu4N(+);M = Mn(II),x = 6,y = 4,Q = Me4N(+);M = Mn(II),x = 5,y = 3,Q = Et4N(+);M = Fe(III),x = 6,y = 3,Q = Me4N(+),Et4N(+),n-Bu4N(+);M = Co(II),x = 4,y = 2,Q = n-Bu4N(+);M = Eu(III),Gd(III),Dy(III),x = 6,y = 3,Q = Bu4N(+))。八面体 Cr(III)盐与先前和新报道的 Fe(III)盐结构相同。Ln(III)阴离子也是八面体的。对于 Mn(II),尽管 Me4N(+)盐是八面体的,但 Et4N(+)盐 Mn(NCS)5具有扭曲的三角双锥几何形状。对于 (Et4N)3[Fe(NCS)6] 和 (n-Bu4N)3[Fe(NCS)6],观察到从红色到绿色的固态尺寸依赖性颜色变化,这归因于结晶样品中的光散射现象。

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