Journal ArticleDOI
Neutral carbene analogues of the heaviest Group 13 elements: Consideration of electronic and steric effects on structure and stability
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TLDR
The structure of the indium complex reveals that replacement of the ligand backbone methyl groups of the previously reported complex with trifluoromethyl substituents results in only minor modifications to the dimensions of the NCCCNIn metallacycle.Abstract:
The neutral monovalent Group 13 β-diketiminato complexes [CH{(CF3)2CN-2,6-iPr2C6H3}2In] and [CH{(Me)2CN-2,6-iPr2C6H3}2Tl] have been synthesised by analogous ‘one-pot’ procedures involving reaction of [KN(SiMe3)2] with the appropriate β-imino-enamine and Group 13 iodide. The structure of the indium complex reveals that replacement of the ligand backbone methyl groups of the previously reported complex [CH{(Me)2CN-2,6-iPr2C6H3}2In] with trifluoromethyl substituents results in only minor modifications to the dimensions of the NCCCNIn metallacycle. The electronic structures of both indium species were interrogated by DFT calculations to reveal similar frontier molecular orbital schemes. In agreement with calculations performed previously on the aluminium and gallium complexes, [CH{(Me)2CN-2,6-iPr2C6H3}2Al] and [CH{(Me)2CN-2,6-iPr2C6H3}2Ga], the HOMO in both indium species comprises a metal-based sp-hybrid while the LUMO is a ligand-based orbital of π symmetry. The vacant indium p-orbital is represented by the LUMO + 1. Although incorporation of the fluorinated substituents results in a stabilisation of the system overall, the stabilities and observed structural features of the complexes are reasoned to be primarily a result of the steric profile of the very bulky ligands and not through any redistribution of the electron density within the cyclic species. The thallium complex is isostructural to the analogous and previously reported aluminium, gallium and indium species. The greater stability of the monovalent state however is reflected in a reordering of the orbital energies and a stabilisation of the metal-based orbitals in the frontier region of the MO scheme.read more
Citations
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N-heterocyclic carbene analogues with low-valent group 13 and group 14 elements: syntheses, structures, and reactivities of a new generation of multitalented ligands.
Journal ArticleDOI
The Chemistry of Aluminum(I), Silicon(II), and Germanium(II)
TL;DR: Although tetrameric Al(I) compounds have been known for a long time, the monomeric carbenes are very recent entrants in Al-I chemistry as discussed by the authors.
Journal ArticleDOI
The chemistry of univalent metal β-diketiminates
TL;DR: The easily electronically and sterically tunable β-diketiminates are widely used auxiliary ligands for the creation of a wide range of metal complexes with various oxidation states in all groups of the periodic table as mentioned in this paper.
Journal ArticleDOI
Four-membered group 13 metal(I) N-heterocyclic carbene analogues: Synthesis, characterization, and theoretical studies
TL;DR: The synthesis, spectroscopic and structural characterization of the monomeric, four-membered group 13 metal(I) heterocycles and an isomeric thallium complex are reported, suggesting they should act as good sigma-donor ligands.
Journal ArticleDOI
Chemistry of aluminium(I)
TL;DR: The presence of a lone pair of electrons plays an important role in the preparation of aluminium containing heterocyclic compounds, main group- main group and transition metal-main group compounds having donor-acceptor bonds by carrying out reactions with unsaturated compounds and Lewis acids.
References
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π-Bonding and the Lone Pair Effect in Multiple Bonds between Heavier Main Group Elements
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Synthesis and Structure of a Monomeric Aluminum(I) Compound [{HC(CMeNAr)2}Al] (Ar=2,6–iPr2C6H3): A Stable Aluminum Analogue of a Carbene
Chunming Cui,Herbert W. Roesky,Hans-Georg Schmidt,Mathias Noltemeyer,Haijun Hao,Fanica Cimpoesu +5 more
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The Tetrameric Aluminum(I) Compound [{Al(η5‐C5Me5)}4]
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How Short is a -Ga⋮Ga- Triple Bond? Synthesis and Molecular Structure of Na2[Mes*2C6H3-Ga⋮Ga-C6H3Mes*2] (Mes* = 2,4,6-i-Pr3C6H2): The First Gallyne
Journal ArticleDOI
Structures, Bonding, and Reaction Chemistry of the Neutral Organogallium(I) Compounds (GaAr)n (n = 1 or 2) (Ar = Terphenyl or Related Ligand): An Experimental Investigation of Ga−Ga Multiple Bonding
TL;DR: The synthesis, structure, and properties of several new organogallium(I) compounds are reported, including one that featured almost linear gallium coordination, Ga-B distances near the sum of the covalent radii of gallium and boron, as well as some close Ga...F contacts.