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Novel halogenated cyclopentasilylene‐2,4‐dienes via DFT
Journal of the Chinese Chemical Society ( IF 1.6 ) Pub Date : 2020-05-18 , DOI: 10.1002/jccs.202000010 Mojgan Ayoubi‐Chianeh 1 , Mohamad Z. Kassaee 1
Journal of the Chinese Chemical Society ( IF 1.6 ) Pub Date : 2020-05-18 , DOI: 10.1002/jccs.202000010 Mojgan Ayoubi‐Chianeh 1 , Mohamad Z. Kassaee 1
Affiliation
In view of immense importance of silylenes and the fact that their properties undergo significant changes on substitution with halogens, here, we have used B3LYP/6‐311++G** level of theory to access the effects of 1–4 halogens (X = F, Cl, Br, and I) on four unprecedented sets of cyclopentasilylene‐2,4‐dienes; with the following formulas: SiC4H3X (1
X), SiC4H2X2 (2
X), SiC4HX3 (3
X), and SiC4X4 (4
X). In going down from F to I, the singlet (s)‐triplet (t) energy gap (ΔEs‐t, a possible indication of stability), and band gap (ΔEH‐L) decrease while nucleophilicity (N), chemical potential (μ), and proton affinity (PA) increase. The overall order of N, μ, and PA for each X is 2
X > 1
X > 3
X > 4
X. Precedence of 2
X over 1
X is attributed to the symmetric cross conjugation in the former. The highest and lowest N are shown by 2
I and 4
F. The trend of divalent angle () for each X is 4
X > 1
X > 3
X > 2
X. The results show that in going from electron withdrawing groups (EWGs) to electron donating groups (EDGs), the ΔEs‐t and ΔEH‐L decrease while N, μ, and PA increase. Also, rather high N of our scrutinized silylenes may suggest new promising ligands in organometallic chemistry.
中文翻译:
通过DFT的新型卤代环戊亚甲硅2,4-二烯
鉴于亚甲硅的重要性及其在被卤素取代后其性能会发生重大变化的事实,在这里,我们使用B3LYP / 6-311 ++ G **的理论水平来研究1-4个卤素的影响(X = F,Cl,Br和I)上的四套史无前例的环戊二烯-2-4-二烯; 具有以下公式:SiC 4 H 3 X(1 X),SiC 4 H 2 X 2(2 X),SiC 4 HX 3(3 X)和SiC 4 X 4(4 X) )。从F下降到I时,单重态(s)-三重态(t)的能隙(ΔEs -t,可能表示稳定性)和带隙(ΔEH -L)减小,而亲核性(N),化学电位(μ)和质子亲和力(PA)增加。的整体顺序Ñ,μ,和PA对于每个X是2 X > 1 X > 3 X > 4 X。2 X优先于1 X归因于前者的对称交叉共轭。最高和最低N表示为 2我和4 ˚F。二价角(趋势),用于每个X是4 X > 1 X > 3 X > 2 X。结果表明,在从吸电子基团(专家工作组)将供电子基团(电子讨论组),则ΔE S-T和ΔE H-L减少而Ñ,μ,和PA增加。同样,N含量很高的受审议的甲硅烷基可能表明在有机金属化学中有新的有前途的配体。
更新日期:2020-05-18
中文翻译:
通过DFT的新型卤代环戊亚甲硅2,4-二烯
鉴于亚甲硅的重要性及其在被卤素取代后其性能会发生重大变化的事实,在这里,我们使用B3LYP / 6-311 ++ G **的理论水平来研究1-4个卤素的影响(X = F,Cl,Br和I)上的四套史无前例的环戊二烯-2-4-二烯; 具有以下公式:SiC 4 H 3 X(1 X),SiC 4 H 2 X 2(2 X),SiC 4 HX 3(3 X)和SiC 4 X 4(4 X) )。从F下降到I时,单重态(s)-三重态(t)的能隙(ΔEs -t,可能表示稳定性)和带隙(ΔEH -L)减小,而亲核性(N),化学电位(μ)和质子亲和力(PA)增加。的整体顺序Ñ,μ,和PA对于每个X是2 X > 1 X > 3 X > 4 X。2 X优先于1 X归因于前者的对称交叉共轭。最高和最低N表示为 2我和4 ˚F。二价角(趋势),用于每个X是4 X > 1 X > 3 X > 2 X。结果表明,在从吸电子基团(专家工作组)将供电子基团(电子讨论组),则ΔE S-T和ΔE H-L减少而Ñ,μ,和PA增加。同样,N含量很高的受审议的甲硅烷基可能表明在有机金属化学中有新的有前途的配体。