Low-valent alkaline-earth metals in all-metal dinuclear metallocenes M2(η5-e5)2 (M = Be, Mg, Ca; E = Sb, Bi)

Congzhi Wang; Nan Li; Yu Xia; Xiuhui Zhang; Maofa Ge; Yan Liu; Qianshu Li

doi:10.1016/j.comptc.2010.10.034

Low-valent alkaline-earth metals in all-metal dinuclear metallocenes M₂(η⁵-e₅)₂ (M = Be, Mg, Ca; E = Sb, Bi)

Congzhi Wang
, Nan Li
, Yu Xia
, Xiuhui Zhang^*
, Maofa Ge
, Yan Liu
, Qianshu Li

^*Corresponding author for this work

Research output: Contribution to journal › Article › peer-review

2 Citations (Scopus)

Abstract

A series of all-metal dinuclear alkaline-earth metallocenes, M₂(η⁵-E₅)₂ (M = Be, Mg, Ca; E = Sb, Bi), have been calculated by the density functional theory (DFT). Natural Bonding Orbital (NBO) analysis indicates that the metal-metal bonds of the title compounds are all single bonds with each metal in its +1 oxidation state, and the bonding between the metal and the all-metal ligand is mainly ionic. For both M₂(η⁵-Sb₅)₂ and M₂(η⁵-Bi₅)₂, the metal-ligand bonds are very strong and the lighter alkaline-earth metal has stronger metal-ligand bonding. By comparing the dissociation energies of metal-metal bond and metal-ligand bond for each M₂(η⁵-E₅)₂, the single metal-metal bond is much weaker than the metal- ligand bond with the same metals. The Mg-Mg bond is the strongest in the M₂(η⁵-Sb₅)₂ and M₂(η⁵-Bi₅)₂ species. Nucleus-independent chemical shifts (NICS) values suggest the planar E₅^- exhibits characteristics of aromaticity in these M₂(η⁵-E₅)₂ species. All the NICS values decrease in the order of Be₂(η⁵-E₅)₂ > Mg₂(η⁵-E₅)₂ > Ca₂(η⁵-E₅)₂ except for the NICS (1.0) values of the M₂(η⁵-Bi₅)₂ (M = Be, Mg, Ca) species. The absolute values of NICS (0.0), NICS (0.5) and NICS (1.0) for M2(η⁵-Sb₅)₂ are larger than those of the corresponding M₂(η⁵-Bi₅)₂.

Original language	English
Pages (from-to)	319-324
Number of pages	6
Journal	Computational and Theoretical Chemistry
Volume	963
Issue number	2-3
DOIs	https://doi.org/10.1016/j.comptc.2010.10.034
Publication status	Published - Feb 2011

Keywords

All-metal
Density functional theory
Dinuclear metallocenes
Low-valent

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10.1016/j.comptc.2010.10.034

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title = "Low-valent alkaline-earth metals in all-metal dinuclear metallocenes M2(η5-e5)2 (M = Be, Mg, Ca; E = Sb, Bi)",

abstract = "A series of all-metal dinuclear alkaline-earth metallocenes, M2(η5-E5)2 (M = Be, Mg, Ca; E = Sb, Bi), have been calculated by the density functional theory (DFT). Natural Bonding Orbital (NBO) analysis indicates that the metal-metal bonds of the title compounds are all single bonds with each metal in its +1 oxidation state, and the bonding between the metal and the all-metal ligand is mainly ionic. For both M2(η5-Sb5)2 and M2(η5-Bi5)2, the metal-ligand bonds are very strong and the lighter alkaline-earth metal has stronger metal-ligand bonding. By comparing the dissociation energies of metal-metal bond and metal-ligand bond for each M2(η5-E5)2, the single metal-metal bond is much weaker than the metal- ligand bond with the same metals. The Mg-Mg bond is the strongest in the M2(η5-Sb5)2 and M2(η5-Bi5)2 species. Nucleus-independent chemical shifts (NICS) values suggest the planar E5- exhibits characteristics of aromaticity in these M2(η5-E5)2 species. All the NICS values decrease in the order of Be2(η5-E5)2 > Mg2(η5-E5)2 > Ca2(η5-E5)2 except for the NICS (1.0) values of the M2(η5-Bi5)2 (M = Be, Mg, Ca) species. The absolute values of NICS (0.0), NICS (0.5) and NICS (1.0) for M2(η5-Sb5)2 are larger than those of the corresponding M2(η5-Bi5)2.",

keywords = "All-metal, Density functional theory, Dinuclear metallocenes, Low-valent",

author = "Congzhi Wang and Nan Li and Yu Xia and Xiuhui Zhang and Maofa Ge and Yan Liu and Qianshu Li",

year = "2011",

month = feb,

doi = "10.1016/j.comptc.2010.10.034",

language = "English",

volume = "963",

pages = "319--324",

journal = "Computational and Theoretical Chemistry",

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TY - JOUR

T1 - Low-valent alkaline-earth metals in all-metal dinuclear metallocenes M2(η5-e5)2 (M = Be, Mg, Ca; E = Sb, Bi)

AU - Wang, Congzhi

AU - Li, Nan

AU - Xia, Yu

AU - Zhang, Xiuhui

AU - Ge, Maofa

AU - Liu, Yan

AU - Li, Qianshu

PY - 2011/2

Y1 - 2011/2

N2 - A series of all-metal dinuclear alkaline-earth metallocenes, M2(η5-E5)2 (M = Be, Mg, Ca; E = Sb, Bi), have been calculated by the density functional theory (DFT). Natural Bonding Orbital (NBO) analysis indicates that the metal-metal bonds of the title compounds are all single bonds with each metal in its +1 oxidation state, and the bonding between the metal and the all-metal ligand is mainly ionic. For both M2(η5-Sb5)2 and M2(η5-Bi5)2, the metal-ligand bonds are very strong and the lighter alkaline-earth metal has stronger metal-ligand bonding. By comparing the dissociation energies of metal-metal bond and metal-ligand bond for each M2(η5-E5)2, the single metal-metal bond is much weaker than the metal- ligand bond with the same metals. The Mg-Mg bond is the strongest in the M2(η5-Sb5)2 and M2(η5-Bi5)2 species. Nucleus-independent chemical shifts (NICS) values suggest the planar E5- exhibits characteristics of aromaticity in these M2(η5-E5)2 species. All the NICS values decrease in the order of Be2(η5-E5)2 > Mg2(η5-E5)2 > Ca2(η5-E5)2 except for the NICS (1.0) values of the M2(η5-Bi5)2 (M = Be, Mg, Ca) species. The absolute values of NICS (0.0), NICS (0.5) and NICS (1.0) for M2(η5-Sb5)2 are larger than those of the corresponding M2(η5-Bi5)2.

AB - A series of all-metal dinuclear alkaline-earth metallocenes, M2(η5-E5)2 (M = Be, Mg, Ca; E = Sb, Bi), have been calculated by the density functional theory (DFT). Natural Bonding Orbital (NBO) analysis indicates that the metal-metal bonds of the title compounds are all single bonds with each metal in its +1 oxidation state, and the bonding between the metal and the all-metal ligand is mainly ionic. For both M2(η5-Sb5)2 and M2(η5-Bi5)2, the metal-ligand bonds are very strong and the lighter alkaline-earth metal has stronger metal-ligand bonding. By comparing the dissociation energies of metal-metal bond and metal-ligand bond for each M2(η5-E5)2, the single metal-metal bond is much weaker than the metal- ligand bond with the same metals. The Mg-Mg bond is the strongest in the M2(η5-Sb5)2 and M2(η5-Bi5)2 species. Nucleus-independent chemical shifts (NICS) values suggest the planar E5- exhibits characteristics of aromaticity in these M2(η5-E5)2 species. All the NICS values decrease in the order of Be2(η5-E5)2 > Mg2(η5-E5)2 > Ca2(η5-E5)2 except for the NICS (1.0) values of the M2(η5-Bi5)2 (M = Be, Mg, Ca) species. The absolute values of NICS (0.0), NICS (0.5) and NICS (1.0) for M2(η5-Sb5)2 are larger than those of the corresponding M2(η5-Bi5)2.

KW - All-metal

KW - Density functional theory

KW - Dinuclear metallocenes

KW - Low-valent

UR - https://www.scopus.com/pages/publications/84855241170

U2 - 10.1016/j.comptc.2010.10.034

DO - 10.1016/j.comptc.2010.10.034

M3 - Article

AN - SCOPUS:84855241170

SN - 2210-271X

VL - 963

SP - 319

EP - 324

JO - Computational and Theoretical Chemistry

JF - Computational and Theoretical Chemistry

IS - 2-3

ER -

Low-valent alkaline-earth metals in all-metal dinuclear metallocenes M₂(η⁵-e₅)₂ (M = Be, Mg, Ca; E = Sb, Bi)

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Keywords

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