ELECTRONIC STRUCTURE OF AG5PB2O6
ELECTRONIC STRUCTURE OF AG5PB2O6
复制标题
AG5PB2O6 的电子结构
DOI：
10.1021/ic00099a033
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发表时间：
1994
影响因子：
4.6
通讯作者：
J. Burdett
中科院分区：
文献类型：
--
作者：
T. D. Brennan;J. Burdett
d10中心之间的成键作用在许多固态和配位化合物中起着重要的作用。d10中心形成键的能力在二聚Pt化合物[Pt（t-Bu）2 P（CH 2）3 P-（？）Bu）2] 2，其中两个铂原子未桥接并且具有2.765 A的键长。1在二聚体和团簇中，d10成键相互作用的形成已经被证明是通过将较高能量的s和p功能混合到主要的d型分子轨道中，导致弱成键相互作用取代闭壳层d10-d10排斥相互作用而发生的。2-5除了配位化学的例子之外，已知许多固态Cu、Ag、Au、Cd和Hg化合物含有金属亚结构，包括链、带、层和3d框架，其形式上含有d10金属，金属-金属距离与相应元素固体中的金属-金属距离相当或甚至更短。5-7在具有Ag-Ag键合的亚结构的银化合物中，有一个亚类的化合物具有形式上的低价（小于1+）银原子并且也属于这类化合物。Ag 2F具有形式上为Ag 1/2+的抗Cdl 2结构8。Ag 30具有明显的（Ag 6）4+团簇的畸变反BiU结构。Ag 6 Ge 10 Pi 2具有更复杂的结构，但也含有10个（Ag 6）4+团簇。另外两种已知的低价富银氧化物是本文的主题Ag 3 Pb 2 O 6，11，12和Bi 4Ag 14 O 12。13银氧化物的电子结构，在几何上与它们的铜非常不同，现地址：摩根州立大学化学系，巴尔的摩，MD 21239。
Bonding interactions between formally d10 centers play an important role in a number of solid-state and coordination compounds. The ability of d10 centers to form bonds is most clearly seen in the dimeric Ptcompound [Pt (f-Bu) 2P (CH2) 3P-(?-Bu) 2] 2, where the two platinum atoms are not bridged and have a bond length of 2.765 A. 1 The formation of d10 bonding interactions in dimers and clusters has been shown to occur by the mixing of higher energy s and p functionsinto predominantly d-type molecular orbitals resulting in the replacement of closedshell d10—d10 repulsive interactions by weakly bonding interactions. 2-5 In addition to examples from coordination chemistry, many solid-state Cu, Ag, Au, Cd, and Hg compounds are known that contain metal substructures, including chains, ribbons, layers, and 3d frameworks that contain formally d10 metals with metal—metal distances comparable to or even shorter than those in the corresponding elemental solids. 5-7 Among the silver compounds with Ag—Ag-bonded substructures, there is a subclass of compounds having formally subvalent (less than 1+) silver atoms and also belonging to this class of compounds. Ag2F has an anti-Cdl2 structure8 with formally Ag1/2+. Ag30 has9 a distorted anti-BiU structure with distinct (Ag6) 4+ clusters. Ag6GeioPi2 has a more complex structure but also contains10 (Ag6) 4+ clusters. The two other known subvalent silver-rich oxides are AgsPb206, 11, 12 the subject of this paper, and Bi4Agi40i2. 13 The electronic structures of silver oxides, geometrically very different from their copper t Present address: Department of Chemistry, Morgan State University, Baltimore, MD 21239.