Structure and bonding in trimetallic arrays containing a Cr-Cr quadruple bond: A challenge to density functional theory
Structure and bonding in trimetallic arrays containing a Cr-Cr quadruple bond: A challenge to density functional theory
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DOI：
10.1016/j.ica.2014.08.061
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发表时间：
2015-01-01
影响因子：
2.8
通讯作者：
McGrady, John E.
中科院分区：
文献类型：
--
作者：
Arcisauskaite, Vaida;Spivak, Mariano;McGrady, John E.
三金属化合物Cr2M(Dpa)(4)Cl-2，M=Cr，Mn，Fe，Ni和Zn的结构趋势为理论处理四重铬铬键提供了一个重要的试验台。铬-铬键长与功能密切相关，反映了不同情况下对交换和关联的不同处理。在Cr2M(Dpa)(4)Cl2-阵列中，顺磁性异质金属的存在通过极化铬-铬西格马键中的自旋密度而延长了铬-铬键，有效地播撒了剩余的pi和Delta组分的局域化。(C)2014爱思唯尔B.V.保留所有权利。
Structural trends within the series of trimetallics Cr2M(dpa)(4)Cl-2, M = Cr, Mn, Fe, Ni and Zn offer an important test bed for the theoretical treatment of the quadruple Cr-Cr bond. Cr-Cr bond lengths are dramatically functional dependent, reflecting the different treatment of exchange and correlation in each case. The presence of a paramagnetic heterometal in a Cr2M(dpa)(4)Cl-2 array has the effect of elongating the Cr-Cr bond by polarising the spin density in the Cr-Cr sigma bond, effectively seeding the localisation of the remaining pi and delta components. (C) 2014 Elsevier B.V. All rights reserved.