含硼二元团簇几何结构与成键特征研究
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摘要
随着计算机技术和计算方法的飞速发展,理论计算已成为预测和研究新型团簇结构与性质的重要手段。近年来,纯硼和含硼二元团簇研究受到广泛关注,但其结构规则和性质变化规律尚不清楚。本文采用密度泛函理论和从头算方法,基于等瓣相似性和等价电子原理,对系列硼氢团簇、碳金团簇、硼金团簇和硼氧团簇的几何结构、成键特征、热力学稳定性及光谱性质等进行了系统研究,为其实验和应用研究提供理论基础。
1.含端η1-Au及桥η2-Au的硼金和碳金团簇
基于从头算理论和密度泛函理论,对BAun-/0(n=1-4)金硼烷的几何结构、电子结构特征和阴离子基态结构的光电子能谱进行了研究。研究发现,BAun-/0(n=1-4)团簇具有与BHn-/0相似的几何结构,进一步证明了H/Au相似性；自然振动理论(NRT)分析证明在BAun-/0簇(n=2-4)中,端η1-Au与中心硼原子间的相互作用主要是共价作用。探讨了BAu4-作为结构单元形成LiBAu4的可能性,为在实验室中合成LiBAu4及其它含有[BAu4]-结构单元的固体无机盐提供了理论基础。
采用密度泛函理论对含双碳的碳金二元团簇C2Aun+(n=1,3,5)和C2Aun(n=2,4)的结构和性质进行了研究。碳金二元团簇低能量异构体中,Au原子既可以作为端η1-Au也可以作为桥η2-Au,其形成规则是：当Au原子数少于3时,Au原子优先选择端配的方式与-C≡C-结合；当Au原子数等于3时,第3个Au原子更倾向于以侧配的方式与Au-C≡C-Au结合形成稳定的路易斯酸碱电子对结构[Au-C≡C-Au]Au+(C2v);当Au原子数超过3时,开始出现-Au3结构单元,该三角形结构单元类似于H,可以采取端配或侧配的不同方式与-C≡C-及Au-C≡C-Au结合。Au3+结构单元的稳定性源于离域3c-2e6键的存在。我们的研究结果将H/Au相似性扩展到H+/Au3+相似性,对于设计含金催化剂和纳米材料具有重要意义。
2.平面π芳香性C3h B6H3+、C2vB10H5-及π反芳香性C2h B8H4
对缺氢体系B2nHn(n=3,4,5)的电子结构和成键特征等进行了研究。研究发现具有完美平面结构、C3h对称性的B6H3+和具有双链结构、C2h对称性的B8H4及C2v对称性的B10H5-,分别对应于环丙烯阳离子D3h C3H3+、环丁二烯D2h C4H4和环戊二烯阴离子D5h C5H5-。平面结构中顶点共享的B3三角形单元相当于环状碳氢化合物中的一个C原子。详细的AdNDP分析和核独立化学位移(NICS)数值分析进一步揭示了该类硼氢化物及其相应碳氢化合物的成键特征和芳香性。
3.芳香性共轭双链硼烯D2h B4H2、C2h B8H2和C2hB12H2
在密度泛函水平上,B2nH2芳香性共轭双链D2h B4H2,C2h B8H2和C2h B12H2均为体系的最低能量异构体,这些链状共轭硼烯分别对应于链状共轭烯烃CnHn+2中的乙烯、1,3-丁二烯和1,3,5-已三烯。共轭硼烯链中的一个B4菱形单元相当于不饱和碳氢链中的一个C=C结构单元。详细的AdNDP和ELF分析结果进一步揭示了该类硼烯的成键特征和芳香性。成键分析还表明,双链状的B3H2-,B5H2-和B6H2有一个离域π轨道,B7H2-,B9H2-和B10H2有两个离域π轨道,B11H2-有三个离域π轨道也分别类似于乙烯、1,3-丁二烯和1,3,5-已三烯。该研究丰富了硼氢化合物和碳氢化合物间的对应关系,有助于理解双链交织全硼纳米结构的稳定性。
基于上述对B8H20/-和B9H20/-结构与性质的研究,进一步分析B8A20/-和B9A20/-(A=Au和BO)的结构及热力学稳定性。研究表明：在双链结构的裸B8-/0和B9-/0团簇两端不饱和B上键合端η1-Au或-BO基,均可以得到完美平面的类似其相应硼氢化合物的基态稳定结构,端η1-Au及-BO基不改变B8-/0和B9-/0骨架及离域π键分布；Au/H相似性及H/BO相似性在BsA2-/0和B9A2-/0(A=H,Au和BO)中依然存在,BO可以作为稳定的结构单元存在于富硼的硼氧化合物中。该计算结果对硼氧化合物或硼金化合物的结构及成键特征研究具有指导作用。
4.含桥η2-BO和η2-BS的B2A60／-团簇(A=BO和BS)
对B2(BO)6和B2(BS)6的几何结构和电子特征及其阴离子的几何结构进行了研究。表明在D2h对称性的B2(Bo)60/-和B2(BS)60/-的稳定结构中,B≡O和B≡S类似于D2h对称性的B2H6中的H原子,既可以作为端基,又可以作为桥基。AdNDP分析进一步揭示了其成键特征。与D3d对称性的B2H6-不同,B2(BO)6-和B2(BS)6-的阴离子的D2h对称性结构稳定,说明B≡O和B≡S与H原子相比,更容易作为桥基。为方便将来的实验室研究,对D2h B2(BO)6和B2(BS)6的红外(IR)和紫外(UV-vis)谱图进行了模拟。该部分的研究与之前我们对硼氧化合物的研究结合在一起,为将来硼的氧化物及硼的硫化物的结构研究进一步拓展了研究思路。
5.环硼氧烷B3O3X3(X=H和BO)及其过渡金属夹心化合物
计算结果表明,B606簇的基态结构与人们所熟知的无机苯D3h B303H3类似,具有和苯相似的几何结构和电子结构。D3h对称性的B3O3(BO)3与B3O3H3都可以作为稳定配体与Cr原子形成热力学上的稳定夹心化合物,Cr原子3d轨道与B3O3X3(X=H,BO)离域π轨道间的相互作用使得系列半夹心、夹心和三层夹心化合物保持稳定。B3O3X3(X=H,BO)配体可以进一步生成[B3O3X3]nCrn-1(X=H,BO)(n≥4)一维链状夹心化合物。本文研究结果引入了一类含B3O3六元环的新颖无机配体,丰富了配位化学的内容。
Along with the rapid development of computer technology and computational methodologies, theoretical computation has become an important way for predicting and studying the structures and characteristics of novel clusters. Recently, pure boron and boron-containing binary clusters have attracted wide attention. However, the rules on structures and properties of the boron-containing binary clusters are not clear. A systematic density functional theory and wave function theory investigation on the geometrical structure, electronic structures, bonding characteristics, thermodynamic stabilities and spectrum characteristics of boron containing binary clusters, such as boron hydrides, boron oxides and boron-gold has been performed in this thesis. We aim to provide a theoretical basis for their experimental and applied researches.
1. Terminal η1-Au and Bridging η2-Au in Boron-gold and Carbon-gold Clusters
An ab initio theoretical investigation on the geometrical, electronic structures and photoelectron specctroscopies (PES) of BAun-/0(n=1-4) clusters has been performed. Density functional theory (DFT) and coupled cluster method (CCSD(T)) calculations indicate that BAun-/0(n=1-4) clusters with n η1-Au possess similar geometrical structures and bonding patterns with the corresponding boron hydrides BHn-/0(n=1-4). Natural resonant theory (NRT) analyses showed that the B-Au interactions in BAun-/0clusters (n=2-4) are mainly covalent. The PES spectra of the BAun-anions and the Au-B stretching vibrations of the BAun neutrals (n=1-4) are simulated. The investigation on BAu4-unit served as the building block provides a theoretical basis for the synthesis of LiBAu4and other [BAu4]--containing inorganic solids.
A systematic density functional theory investigation on C2Aun+(n=1,3,5) and C2Aun (n=2,4,6) indicates that gold atoms serve as terminal η1-Au in the chain-like Cs C2Au+(C=C-Au+) and D∞h C2Au2(Au-C=C-Au) and as bridging η2-Au in the side-on coordinated C2v C2Au3+([Au-C=C-Au]Au+) and Cs C2HAu2+([Au-C=C-Au]Au+). However, when the number of gold atoms reaches four, they form stable gold triangles (-Au3) in the head-on coordinated C2v C2Au4(Au-C=C+Au3) and the side-on coordinated C2v C2Au5+([Au-C=C-Au]Au3+. The high stability of Au3triangles originates from the fact that an equilateral D3h Au3+cation possesses a completely delocalized three-center-two-electron (3c-2e) σ bond and therefore is σ-aromatic in nature. The extension from H/Au analogy to H/Au3analogy established in this work may have important implications in designing new gold-containing catalysts and nano-materials.
2. Planar π-aromatic C3h B6H3+, C2v B10H5-and π-antiaromatic C2h B8H4
Extensive structural searches and wave function theory calculations have been performed for B2nHn(n=3,4,5). We predict the existence of the perfectly planar triangle C3h B6H3+, the double-chain C2h B8H4and the planar C2v B10H5-which are the inorganic analogues of cyclopropene cation D3h C3H3+, cyclobutadiene D2h C4H4, and cyclopentadiene D5h C5H5-in both geometrical and electronic structures, respectively. Here, a vertex-sharing B3triangle in planar boron hydride clusters is equivalent to a C atom in the well-known hydrocarbon clusters. Detailed adaptive natural density partitioning (AdNDP) and the nucleus independent chemical shifts (NICS) analyses further unravel the bonding patterns and overall aromaticity of C3h B6H3+, C2h B8H4and C2v B10H5-.
3. Aromatic Double-Chain Conjugated D2h B4H2, C2h B8H2and C2h B12H2
Based upon comprehensive theoretical investigations and known experimental observations, we predict the existence of the aromatic double-chain (DC) planar D2h B4H2, C2h B8H2and C2h B12H2which all appear to be the lowest-lying isomers of the systems at DFT level. These conjugated aromatic borenes turn out to be the boron hydride analogues of the conjugated ethylene D2h C2H4,1,3-butadiene C2h C4H6, and1,3,5-hexatriene C2h C6H8, respectively, indicating that a B4rhombus in B2nH2borenes (n=2,4,6) is equivalent to a C=C double bond unit in the corresponding CnHn+2hydrocarbons. Detailed canonical molecular orbital (CMO), AdNDP, and electron localization function (ELF) analyses unravel the bonding patterns of these novel borene clusters and indicate that they are all overall aromatic in nature with the formation of islands of both σ-and π-aromaticity. The double-chain planar or quasi-planar C2v B3H2-, C2B5H2-, and C2h B6H2with one delocalized π orbital, C2v B7H2-, C2B9H2-, and C2h B10H2with two delocalized π orbitals, and C2v B11H2-with three delocalized π orbitals are found to be analogous in π-bonding to D2h B4H2, C2h B8H2, and C2h B12H2, respectively. The results obtained in this work enrich the analogous relationship between hydroborons and their hydrocarbon counterparts and help to understand the high stability of all-boron nanostructures which favor the formation of double-chain substructures.
Theoretical evidences strongly suggest that the ground states of the BnA20/-(n=8,9; A=Au and BO) all can be obtained by connecting two terminal η1-Au or η1-BO to the corner B atoms. The distributions of the localized π bonds of the B8and B9skeleton have not been changed by the terminal η1-Au or η1-BO. The Au/H and H/BO analogy all still exist in BnA20/-(n=8,9; A=H,Au and BO). The BO group exists as stable unit in the boron-rich boron oxide.
4. B2A60/-(A=BO and BS) Clusters with Bridging η2-BO or η2-BS
The investigation on the geometrical and electronic properties of B2(BO)60/-and B2(BS)60/-have been performed by density functional theory (DFT) using the B3LYP and BP86methods, for comparison of their predicted structures with those of the well known B2H6. Similar to H atoms in the corresponding boranes, both BO and BS units can serve as terminal and bridging groups in D2h B2(BO)60/-and B2(BS)60/-,respectively. As analogues of diborane (B2H6), D2h B2(BO)6and B2(BS)6with two bridging η2-BO or η2-BS groups are the most interesting candidates possible to be targeted in future experiments. AdNDP analyses further unravel the bonding patterns. Different from that of classical D3d B2H6-,D2h B2(BO)6-and B2(BS)6-with two bridging η2-BO or η2-BS groups are more stable than their corresponding D3d structures. The IR spectra and UV-vis spectra of D2h B2(BO)6and B2(BS)6have been simulated to facilitate their future experimental characterizations. The boronyl pattern we proposed builds a clear structural link between boron oxides or boron sulfides and boron hydrides.
5. Boroxine B3O3X3(X=H and BO) Clusters and Their Transition-metal Sandwich Compounds
Based upon extensive density functional theory calculations, molecular analyses and natural resonance theory (NRT) analyses, we predict the existence of the perfectly planar D3h B6O6(1,1A1') we prefer to as boronyl boroxine which is the ground states of the systems and the boron oxide analogue of benzene D6h C6H6.A density functional theory investigation on half-sandwich-type C3v B3O3X3Cr, full-sandwich-type D3d [B3O3X3]2Cr, and triple-decker complexes [B3O3X3]3Cr2(X=H, BO) containing B3O3H3or B3O3(BO)3ligands has been performed. Both B3O3H3and B3O3(BO)3units serve as robust inorganic ligands in B3O3X3Cr,[B3O3X3]2Cr and [B3O3X3]3Cr2(X=H, BO) complex series. Effective d-π coordination interactions between the partially filled3d orbitals of the transition-metal center and the delocalized π orbitals of the B3O3X3(X=H, BO) ligands help maintain the stabilities of the complexes. The sandwich structural pattern developed in this work expands the structural domain of transition-metal complexes by introducing new inorganic B3O3H3and B3O3(BO)3with a B3O3core into traditional sandwich-type structures and may be extended to form [B3O3X3]nCrn-1(X=H, BO) multi-decker (n≥4) liner wires.
1.含端η1-Au及桥η2-Au的硼金和碳金团簇
基于从头算理论和密度泛函理论,对BAun-/0(n=1-4)金硼烷的几何结构、电子结构特征和阴离子基态结构的光电子能谱进行了研究。研究发现,BAun-/0(n=1-4)团簇具有与BHn-/0相似的几何结构,进一步证明了H/Au相似性；自然振动理论(NRT)分析证明在BAun-/0簇(n=2-4)中,端η1-Au与中心硼原子间的相互作用主要是共价作用。探讨了BAu4-作为结构单元形成LiBAu4的可能性,为在实验室中合成LiBAu4及其它含有[BAu4]-结构单元的固体无机盐提供了理论基础。
采用密度泛函理论对含双碳的碳金二元团簇C2Aun+(n=1,3,5)和C2Aun(n=2,4)的结构和性质进行了研究。碳金二元团簇低能量异构体中,Au原子既可以作为端η1-Au也可以作为桥η2-Au,其形成规则是：当Au原子数少于3时,Au原子优先选择端配的方式与-C≡C-结合；当Au原子数等于3时,第3个Au原子更倾向于以侧配的方式与Au-C≡C-Au结合形成稳定的路易斯酸碱电子对结构[Au-C≡C-Au]Au+(C2v);当Au原子数超过3时,开始出现-Au3结构单元,该三角形结构单元类似于H,可以采取端配或侧配的不同方式与-C≡C-及Au-C≡C-Au结合。Au3+结构单元的稳定性源于离域3c-2e6键的存在。我们的研究结果将H/Au相似性扩展到H+/Au3+相似性,对于设计含金催化剂和纳米材料具有重要意义。
2.平面π芳香性C3h B6H3+、C2vB10H5-及π反芳香性C2h B8H4
对缺氢体系B2nHn(n=3,4,5)的电子结构和成键特征等进行了研究。研究发现具有完美平面结构、C3h对称性的B6H3+和具有双链结构、C2h对称性的B8H4及C2v对称性的B10H5-,分别对应于环丙烯阳离子D3h C3H3+、环丁二烯D2h C4H4和环戊二烯阴离子D5h C5H5-。平面结构中顶点共享的B3三角形单元相当于环状碳氢化合物中的一个C原子。详细的AdNDP分析和核独立化学位移(NICS)数值分析进一步揭示了该类硼氢化物及其相应碳氢化合物的成键特征和芳香性。
3.芳香性共轭双链硼烯D2h B4H2、C2h B8H2和C2hB12H2
在密度泛函水平上,B2nH2芳香性共轭双链D2h B4H2,C2h B8H2和C2h B12H2均为体系的最低能量异构体,这些链状共轭硼烯分别对应于链状共轭烯烃CnHn+2中的乙烯、1,3-丁二烯和1,3,5-已三烯。共轭硼烯链中的一个B4菱形单元相当于不饱和碳氢链中的一个C=C结构单元。详细的AdNDP和ELF分析结果进一步揭示了该类硼烯的成键特征和芳香性。成键分析还表明,双链状的B3H2-,B5H2-和B6H2有一个离域π轨道,B7H2-,B9H2-和B10H2有两个离域π轨道,B11H2-有三个离域π轨道也分别类似于乙烯、1,3-丁二烯和1,3,5-已三烯。该研究丰富了硼氢化合物和碳氢化合物间的对应关系,有助于理解双链交织全硼纳米结构的稳定性。
基于上述对B8H20/-和B9H20/-结构与性质的研究,进一步分析B8A20/-和B9A20/-(A=Au和BO)的结构及热力学稳定性。研究表明：在双链结构的裸B8-/0和B9-/0团簇两端不饱和B上键合端η1-Au或-BO基,均可以得到完美平面的类似其相应硼氢化合物的基态稳定结构,端η1-Au及-BO基不改变B8-/0和B9-/0骨架及离域π键分布；Au/H相似性及H/BO相似性在BsA2-/0和B9A2-/0(A=H,Au和BO)中依然存在,BO可以作为稳定的结构单元存在于富硼的硼氧化合物中。该计算结果对硼氧化合物或硼金化合物的结构及成键特征研究具有指导作用。
4.含桥η2-BO和η2-BS的B2A60／-团簇(A=BO和BS)
对B2(BO)6和B2(BS)6的几何结构和电子特征及其阴离子的几何结构进行了研究。表明在D2h对称性的B2(Bo)60/-和B2(BS)60/-的稳定结构中,B≡O和B≡S类似于D2h对称性的B2H6中的H原子,既可以作为端基,又可以作为桥基。AdNDP分析进一步揭示了其成键特征。与D3d对称性的B2H6-不同,B2(BO)6-和B2(BS)6-的阴离子的D2h对称性结构稳定,说明B≡O和B≡S与H原子相比,更容易作为桥基。为方便将来的实验室研究,对D2h B2(BO)6和B2(BS)6的红外(IR)和紫外(UV-vis)谱图进行了模拟。该部分的研究与之前我们对硼氧化合物的研究结合在一起,为将来硼的氧化物及硼的硫化物的结构研究进一步拓展了研究思路。
5.环硼氧烷B3O3X3(X=H和BO)及其过渡金属夹心化合物
计算结果表明,B606簇的基态结构与人们所熟知的无机苯D3h B303H3类似,具有和苯相似的几何结构和电子结构。D3h对称性的B3O3(BO)3与B3O3H3都可以作为稳定配体与Cr原子形成热力学上的稳定夹心化合物,Cr原子3d轨道与B3O3X3(X=H,BO)离域π轨道间的相互作用使得系列半夹心、夹心和三层夹心化合物保持稳定。B3O3X3(X=H,BO)配体可以进一步生成[B3O3X3]nCrn-1(X=H,BO)(n≥4)一维链状夹心化合物。本文研究结果引入了一类含B3O3六元环的新颖无机配体,丰富了配位化学的内容。
Along with the rapid development of computer technology and computational methodologies, theoretical computation has become an important way for predicting and studying the structures and characteristics of novel clusters. Recently, pure boron and boron-containing binary clusters have attracted wide attention. However, the rules on structures and properties of the boron-containing binary clusters are not clear. A systematic density functional theory and wave function theory investigation on the geometrical structure, electronic structures, bonding characteristics, thermodynamic stabilities and spectrum characteristics of boron containing binary clusters, such as boron hydrides, boron oxides and boron-gold has been performed in this thesis. We aim to provide a theoretical basis for their experimental and applied researches.
1. Terminal η1-Au and Bridging η2-Au in Boron-gold and Carbon-gold Clusters
An ab initio theoretical investigation on the geometrical, electronic structures and photoelectron specctroscopies (PES) of BAun-/0(n=1-4) clusters has been performed. Density functional theory (DFT) and coupled cluster method (CCSD(T)) calculations indicate that BAun-/0(n=1-4) clusters with n η1-Au possess similar geometrical structures and bonding patterns with the corresponding boron hydrides BHn-/0(n=1-4). Natural resonant theory (NRT) analyses showed that the B-Au interactions in BAun-/0clusters (n=2-4) are mainly covalent. The PES spectra of the BAun-anions and the Au-B stretching vibrations of the BAun neutrals (n=1-4) are simulated. The investigation on BAu4-unit served as the building block provides a theoretical basis for the synthesis of LiBAu4and other [BAu4]--containing inorganic solids.
A systematic density functional theory investigation on C2Aun+(n=1,3,5) and C2Aun (n=2,4,6) indicates that gold atoms serve as terminal η1-Au in the chain-like Cs C2Au+(C=C-Au+) and D∞h C2Au2(Au-C=C-Au) and as bridging η2-Au in the side-on coordinated C2v C2Au3+([Au-C=C-Au]Au+) and Cs C2HAu2+([Au-C=C-Au]Au+). However, when the number of gold atoms reaches four, they form stable gold triangles (-Au3) in the head-on coordinated C2v C2Au4(Au-C=C+Au3) and the side-on coordinated C2v C2Au5+([Au-C=C-Au]Au3+. The high stability of Au3triangles originates from the fact that an equilateral D3h Au3+cation possesses a completely delocalized three-center-two-electron (3c-2e) σ bond and therefore is σ-aromatic in nature. The extension from H/Au analogy to H/Au3analogy established in this work may have important implications in designing new gold-containing catalysts and nano-materials.
2. Planar π-aromatic C3h B6H3+, C2v B10H5-and π-antiaromatic C2h B8H4
Extensive structural searches and wave function theory calculations have been performed for B2nHn(n=3,4,5). We predict the existence of the perfectly planar triangle C3h B6H3+, the double-chain C2h B8H4and the planar C2v B10H5-which are the inorganic analogues of cyclopropene cation D3h C3H3+, cyclobutadiene D2h C4H4, and cyclopentadiene D5h C5H5-in both geometrical and electronic structures, respectively. Here, a vertex-sharing B3triangle in planar boron hydride clusters is equivalent to a C atom in the well-known hydrocarbon clusters. Detailed adaptive natural density partitioning (AdNDP) and the nucleus independent chemical shifts (NICS) analyses further unravel the bonding patterns and overall aromaticity of C3h B6H3+, C2h B8H4and C2v B10H5-.
3. Aromatic Double-Chain Conjugated D2h B4H2, C2h B8H2and C2h B12H2
Based upon comprehensive theoretical investigations and known experimental observations, we predict the existence of the aromatic double-chain (DC) planar D2h B4H2, C2h B8H2and C2h B12H2which all appear to be the lowest-lying isomers of the systems at DFT level. These conjugated aromatic borenes turn out to be the boron hydride analogues of the conjugated ethylene D2h C2H4,1,3-butadiene C2h C4H6, and1,3,5-hexatriene C2h C6H8, respectively, indicating that a B4rhombus in B2nH2borenes (n=2,4,6) is equivalent to a C=C double bond unit in the corresponding CnHn+2hydrocarbons. Detailed canonical molecular orbital (CMO), AdNDP, and electron localization function (ELF) analyses unravel the bonding patterns of these novel borene clusters and indicate that they are all overall aromatic in nature with the formation of islands of both σ-and π-aromaticity. The double-chain planar or quasi-planar C2v B3H2-, C2B5H2-, and C2h B6H2with one delocalized π orbital, C2v B7H2-, C2B9H2-, and C2h B10H2with two delocalized π orbitals, and C2v B11H2-with three delocalized π orbitals are found to be analogous in π-bonding to D2h B4H2, C2h B8H2, and C2h B12H2, respectively. The results obtained in this work enrich the analogous relationship between hydroborons and their hydrocarbon counterparts and help to understand the high stability of all-boron nanostructures which favor the formation of double-chain substructures.
Theoretical evidences strongly suggest that the ground states of the BnA20/-(n=8,9; A=Au and BO) all can be obtained by connecting two terminal η1-Au or η1-BO to the corner B atoms. The distributions of the localized π bonds of the B8and B9skeleton have not been changed by the terminal η1-Au or η1-BO. The Au/H and H/BO analogy all still exist in BnA20/-(n=8,9; A=H,Au and BO). The BO group exists as stable unit in the boron-rich boron oxide.
4. B2A60/-(A=BO and BS) Clusters with Bridging η2-BO or η2-BS
The investigation on the geometrical and electronic properties of B2(BO)60/-and B2(BS)60/-have been performed by density functional theory (DFT) using the B3LYP and BP86methods, for comparison of their predicted structures with those of the well known B2H6. Similar to H atoms in the corresponding boranes, both BO and BS units can serve as terminal and bridging groups in D2h B2(BO)60/-and B2(BS)60/-,respectively. As analogues of diborane (B2H6), D2h B2(BO)6and B2(BS)6with two bridging η2-BO or η2-BS groups are the most interesting candidates possible to be targeted in future experiments. AdNDP analyses further unravel the bonding patterns. Different from that of classical D3d B2H6-,D2h B2(BO)6-and B2(BS)6-with two bridging η2-BO or η2-BS groups are more stable than their corresponding D3d structures. The IR spectra and UV-vis spectra of D2h B2(BO)6and B2(BS)6have been simulated to facilitate their future experimental characterizations. The boronyl pattern we proposed builds a clear structural link between boron oxides or boron sulfides and boron hydrides.
5. Boroxine B3O3X3(X=H and BO) Clusters and Their Transition-metal Sandwich Compounds
Based upon extensive density functional theory calculations, molecular analyses and natural resonance theory (NRT) analyses, we predict the existence of the perfectly planar D3h B6O6(1,1A1') we prefer to as boronyl boroxine which is the ground states of the systems and the boron oxide analogue of benzene D6h C6H6.A density functional theory investigation on half-sandwich-type C3v B3O3X3Cr, full-sandwich-type D3d [B3O3X3]2Cr, and triple-decker complexes [B3O3X3]3Cr2(X=H, BO) containing B3O3H3or B3O3(BO)3ligands has been performed. Both B3O3H3and B3O3(BO)3units serve as robust inorganic ligands in B3O3X3Cr,[B3O3X3]2Cr and [B3O3X3]3Cr2(X=H, BO) complex series. Effective d-π coordination interactions between the partially filled3d orbitals of the transition-metal center and the delocalized π orbitals of the B3O3X3(X=H, BO) ligands help maintain the stabilities of the complexes. The sandwich structural pattern developed in this work expands the structural domain of transition-metal complexes by introducing new inorganic B3O3H3and B3O3(BO)3with a B3O3core into traditional sandwich-type structures and may be extended to form [B3O3X3]nCrn-1(X=H, BO) multi-decker (n≥4) liner wires.
引文
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