Significant geometry and charge difference between the E54- bare clusters of group 14 Zintl anions and their coordinated form in [E5{M(CO)3}2]4- (E = Si, Ge, Sn, Pb; M = Cr, Mo, W) complexes

被引：11

作者：

Gholiee, Yasin ^{[1
]}

Salehzadeh, Sadegh ^{[2
]}

Khodaveisi, Shiva ^{[2
]}

机构：

[1] Malayer Univ, Fac Sci, Dept Chem, Malayer, Iran

[2] Bu Ali Sina Univ, Fac Chem, Hamadan, Iran

来源：

NEW JOURNAL OF CHEMISTRY | 2019年 / 43卷 / 20期

关键词：

DENSITY-FUNCTIONAL THEORY; STABLE HOMOPOLYATOMIC ANIONS; HOST-GUEST CHEMISTRY; CRYSTAL-STRUCTURES; GERMANIUM CLUSTERS; IONS; ELEMENTS; PENTAPLUMBIDE(2-); APPROXIMATION; AZACRYPTANDS;

D O I：

10.1039/c9nj00162j

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

In this paper, at first, the possible structures for E-5(n) Zintl ions (E = Si, Ge, Sn, Pb; n = 0, 2-, 4-) were investigated at the BP86/def2-TZVPP and M06-2X/def2-TZVPP levels of theory. The results showed that E-5(2-) bare clusters, in agreement with their solid state structures, have the minimum energy in the trigonal bipyramid (D-3h), while the neutral E-5 and also E-5(4-) ions, which have not been characterized structurally to date, are stabilized in the oblate trigonal bipyramid (D-3h) and square pyramid (C-4v) geometries, respectively. Then [E-5{M(CO)(3)}(2)](4-) complexes (M = Cr, Mo, W) containing a planar E-5(4-) ring were investigated at the same levels of theory. The results show that the strong interaction of the planar E-5(4-) ring with the two {M(CO)(3)} fragments and significant charge donation from it is the reason for its strained planar geometry. This was further confirmed by NBO and Energy Decomposition Analysis-Natural Orbital for Chemical Valence (EDA-NOCV) as well as analysis of carbonyl vibrational frequencies. The EDA analysis indicated that the interaction energy values (E-int) in the series of these complexes show the same trend as the term for orbital interactions (E-orb).

引用

页码：7797 / 7805

页数：9

共 23 条

[1] [Ge9{M(CO)5}3]4-: electrophilic addition of M(CO)5 and [E9]4- Zintl anions (M = Cr, Mo, W)
Wang, Lulu
Wang, Yi
Li, Zhenyu
Ruan, Huapeng
Xu, Li
[J]. DALTON TRANSACTIONS, 2017, 46 (21) : 6839 - 6842
[2] Syntheses, crystal structures, and density functional theory calculations of the closo-[1-M(CO)3(η4-E9)]4- (E = Sn, Pb; M = Mo, W) cluster anions and solution NMR spectroscopic characterization of [1-M(CO)3(η4-Sn9)]4-(M = Cr, Mo, W)
Campbell, J
Mercier, HPA
Franke, H
Santry, DP
Dixon, DA
Schrobilgen, GJ
[J]. INORGANIC CHEMISTRY, 2002, 41 (01) : 86 - 107
[3] Mechanisms for the Reactions of Group 10 Transition Metal Complexes with Metal Group 14 Element Bonds, Bbt(Br)E=M(PCy3)2 (E = C, Si, Ge, Sn, Pb; M = Pd and Pt)
Liao, Wei-Hung
Ho, Pei-Yun
Su, Ming-Der
[J]. INORGANIC CHEMISTRY, 2013, 52 (03) : 1338 - 1348
[4] Theoretical investigation of triple bonding between transition metal and main group elements in η5-C5H5(CO)2MER (M = Cr, Mo, W;: E = Si, Ge, Sn, Pb; R = terphenyl groups)
Takagi, N
Yamazaki, K
Nagase, S
[J]. BULLETIN OF THE KOREAN CHEMICAL SOCIETY, 2003, 24 (06) : 832 - 836
[5] Linear ME-Me Versus Bent M-E-Me: Bonding Analysis in Heavier Metal-ylidyne Complexes [(Cp)(CO)2MEMe] and Metallo-ylidenes [(Cp)(CO)3M-EMe] (M = Cr, Mo, W; E = Si, Ge, Sn, Pb)
Pandey, Krishna K.
Lledos, Agusti
[J]. INORGANIC CHEMISTRY, 2009, 48 (07) : 2748 - 2759
[6] Transition metal Fischer-type complexes. Density functional analysis of the systems (CO)(5)Cr=EH(2) (E=C, Si, Ge, Sn) and (CO)(5)M=CH2 (M=Mo, W, Mn+)
Jacobsen, H
Ziegler, T
[J]. INORGANIC CHEMISTRY, 1996, 35 (03) : 775 - 783
[7] Nature of C → E and ME bonds in [Cp(CO)2ME ← NHC(R)]+ (E = Si, Ge, Sn, pb; M: Cr, Mo, w; R = H, F, Cl, Br, CH3, Ph, dipp, Si(CH3)3) complexes
Khodadadi, Farzaneh
Bayat, Mehdi
Salehzadeh, Sadegh
Soltani, Elham
[J]. POLYHEDRON, 2021, 193
[8] Transition-Metal Complexes [(PMe3)2Cl2M(E)] and [(PMe3)2(CO)2M(E)] with Naked Group 14 Atoms (E = C-Sn) as Ligands; Part 2: Complexation with W(CO)5
Parameswaran, Pattiyil
Frenking, Gernot
[J]. CHEMISTRY-A EUROPEAN JOURNAL, 2009, 15 (35) : 8817 - 8824
[9] Transition Metal Fischer-Type Complexes. Density Functional Analysis of the Systems (CO)5Cr=EH2 (E = C, Si, Ge, Sn) and (CO)5M=CH2 (M = Mo, W, Mn+)
Jacobsen, H.
Ziegler, T.
[J]. Inorganic Chemistry, 35 (03):
[10] Germylene and stannylene (Me2NCH2CH2O)2E as strong σ-donor ligands for transition metal complexes [ML(CO)n] (E = Ge, Sn; M = Cr, Mo, W, n=4 or 5; M = Fe, n=4). Synthesis, spectroscopic and theoretical study
Portnyagin, Ivan A.
Nechaev, Mikhail S.
[J]. JOURNAL OF ORGANOMETALLIC CHEMISTRY, 2009, 694 (19) : 3149 - 3153

← 1 2 3 →