Nature of E–E bonds in heavier ditetrel alkyne analogues ArEEAr (Ar = C6H3-2,6(C6H3-2,6-Pri2)2; E = Si, Ge, Sn, and Pb)

Huo, Suhong; Li, Xiaoyan; Zeng, Yanli; Sun, ZhengMing; Zheng, Shourong; Meng, Lingpeng

doi:10.1039/c3nj00600j

Cited by 12 publications

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“…In fact, this single bonding pattern has been used to explain the strongly bent distannyne. ,, Consistent with the accumulation of the electron density at metal centers, Landis and Weinhold showed the important role of resonance configurations II′ and III′ in heavier group 14 HMMH by natural resonance theory (NRT) calculations . In addition, VB theory, electron localization function (ELF), ,,, and quantum theory of atoms in molecules (QTAIM) method ,, have been used to analyze the multiple bonding in heavier group 13 or 14 analogues of alkene and alkyne, some of which display charge-shift characters. − …”

Section: Introductionsupporting

confidence: 75%

“…The study of compounds with multiple bonds between heavier 13 and 14 main group elements (metals) is one of the central themes in organometallic and inorganic chemistry due to their unusual bonding, high reactivity, and potential applications in catalysis. − The heavier group 13 or 14 analogues of alkene or alkyne are markedly different from the much familiar planar and linear structures of boron and carbon congeners and possess either pyramidalized or trans -bent structures (Figure ). − The striking difference between light (nonmetal) and heavy (metal) elements makes the nature of their multiple bonds uncertain and hence heatedly debated. ,− Several bonding models proposed for the heavier alkene and alkyne analogues are shown in Figure . For distannene [(Me 3 Si) 2 CH] 2 SnSn[CH(SiMe 3 ) 2 ] 2 , Lappert and co-workers proposed the donor–acceptor model which can be illustrated with valence bond (VB) structures II and III in Figure a. ,− Similarly, Trinquier et al used VB interpretation of CASSCF results to examine the contributions from the ionic structures apart from the coupled π-diradical ( I in Figure a) structure to the ground state.…”

Section: Introductionmentioning

confidence: 99%

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Side-On versus End-On Binding Modes between Metal Cations and (NHC)AlAl(NHC)

et al. 2020

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Group 13 or 14 analogues of alkene or alkyne are characterized with unusual bonding, high reactivity, and potential applications in catalysis, but few studies have ever addressed their bonding modes with metal cations. The unique behaviors of heavier group 13 or 14 ethyne analogues inspire us to hypothesize the existence of their end-on complexation with metal cations. Here we computationally studied the interactions of the lightest metal alkyne analogue in group 13, (NHC)AlAl(NHC), with alkali metal cations Li + , Na + , and K + and transition metal cations Cu + , Ag + , and Au + . The quantum chemical bonding analysis shows that only the side-on binding mode is feasible in complexes with alkali metal cations. In contrast, complexes with transition metal cations prefer the end-on bonding mode, where pronounced covalent (dative) character is identified based on the bond distances, charge transfer, and topological properties at the bond critical points (BCPs). It can be interpreted with the electron promotion (excitation) and the subsequent σ donation from the lone pairs of Al to the s orbitals of transition metal cations. Further studies show that replacing the substituent NHC by phenyl anion has little impact on the end-on binding mode. Similar results can be found for disilynes.

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Section: Introductionsupporting

confidence: 75%

Section: Introductionmentioning

confidence: 99%

Side-On versus End-On Binding Modes between Metal Cations and (NHC)AlAl(NHC)

et al. 2020

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“…Triple bonds between heavier main group atoms have been calculated to involve considerable CS character. , These bonds have been studied by a topological analysis of parameters such as the electron localization functions and the delocalization index from the atoms in molecules theory as well as an analysis of the orbitals constituting the bond. As expected from earlier VB and MO calculations, these show that the multiple bonds between the heavier atoms differ markedly from those between the lighter, second period elements such as carbon, nitrogen, and oxygen.…”

Section: New Aspects Of Bonding Main-group-element Compoundsmentioning

confidence: 99%

“…The calculated AIM parameters for the group 14 series of formula ArEEAr (E = C–Pb, Ar = terphenyl ligand) show that the bonds display CS character. Table summarizes an AIM analysis of the E–E bonding at bond critical points (the point along the bond line or path between the E–E-bonded atoms where the electron density is maximal. The calculated electron density ρ( r c ) shows a large drop to a relatively low level on going from carbon to silicon, which drops further with increasing E atomic number.…”

Section: New Aspects Of Bonding Main-group-element Compoundsmentioning

confidence: 99%

An Update on Multiple Bonding between Heavier Main Group Elements: The Importance of Pauli Repulsion, Charge-Shift Character, and London Dispersion Force Effects

Power

2020

Organometallics

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An update on some recent developments in the bonding of compounds with multiple bonds between heavier main group elements is the major theme of this review. A brief historical summary of the field is given in the Introduction. This is followed by a discussion of the major factors affecting the multiple bonding between these elements and the approaches used in the interpretation of that bonding. This organizational format follows that used in two earlier comprehensive reviews covering the area. However, this review is not a comprehensive one and it concerns compounds with homonuclear multiple bonds only. It emphasizes two new themes which involve London dispersion force (LDF) energies and charge-shift (CS) effects that were not treated in the earlier reviews. Although LDF effects are always present in molecular species, it is now clear they can be of decisive importance in the stability of the multiple-bonded compounds, especially those where the multiple bond is weak.

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“…Gibbs interaction energy of −429 kJ mol –1 taking into account fragment relaxation) with significant stabilization, –89 kJ mol –1 , from dispersion interactions. The possibility of charge-shift character in the Al–N bond has not yet been supported by computational data. − …”

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A Monomeric Aluminum Imide (Iminoalane) with Al–N Triple-Bonding: Bonding Analysis and Dispersion Energy Stabilization

et al. 2021

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The reaction of :AlAr i Pr8 (Ar i Pr8 = C 6 H-2,6-(C 6 H 2 -2,4,6- i Pr 3 ) 2 -3,5- i Pr 2 ) with Ar Me6 N 3 (Ar Me6 = C 6 H 3 -2,6-(C 6 H 2 -2,4,6-Me 3 ) 2 ) in hexanes at ambient temperature gave the aluminum imide Ar i Pr8 AlNAr Me6 ( 1 ). Its crystal structure displayed short Al–N distances of 1.625(4) and 1.628(3) Å with linear (C–Al–N–C = 180°) or almost linear (C–Al–N = 172.4(2)°; Al–N–C = 172.5(3)°) geometries. DFT calculations confirm linear geometry with an Al–N distance of 1.635 Å. According to energy decomposition analysis, the Al–N bond has three orbital components totaling −1350 kJ mol –1 and instantaneous interaction energy of −551 kJ mol –1 with respect to :AlAr i Pr8 and Ar Me6 N̈:. Dispersion accounts for −89 kJ mol –1 , which is similar in strength to one Al–N π-interaction. The electronic spectrum has an intense transition at 290 nm which tails into the visible region. In the IR spectrum, the Al–N stretching band is calculated to appear at ca. 1100 cm –1 . In contrast, reaction of :AlAr i Pr8 with 1-AdN 3 or Me 3 SiN 3 gave transient imides that immediately reacted with a second equivalent of the azide to give Ar i Pr8 Al[(NAd) 2 N 2 ] ( 2 ) or Ar i Pr8 Al(N 3 ){N(SiMe 3 ) 2 } ( 3 ).

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Nature of E–E bonds in heavier ditetrel alkyne analogues ArEEAr (Ar = C6H3-2,6(C6H3-2,6-Pri2)2; E = Si, Ge, Sn, and Pb)

Cited by 12 publications

References 50 publications

Side-On versus End-On Binding Modes between Metal Cations and (NHC)AlAl(NHC)

Side-On versus End-On Binding Modes between Metal Cations and (NHC)AlAl(NHC)

An Update on Multiple Bonding between Heavier Main Group Elements: The Importance of Pauli Repulsion, Charge-Shift Character, and London Dispersion Force Effects

A Monomeric Aluminum Imide (Iminoalane) with Al–N Triple-Bonding: Bonding Analysis and Dispersion Energy Stabilization

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