Coordination of indium monohalide with group-10 metal carbonyls [TM(CO) 3 (InX)]: a DFT study
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ORIGINAL PAPER
Coordination of indium monohalide with group‑10 metal carbonyls [TM(CO)3(InX)]: a DFT study Paularokiadoss Francis1,2 · Sekar Alagan1 · Christopher Jeyakumar Thayalraj3 Received: 18 April 2020 / Accepted: 25 July 2020 © Institute of Chemistry, Slovak Academy of Sciences 2020
Abstract A DFT study carried out on the diatomic ligand of InX coordinated with metal carbonyls [TM(InX)(CO)3] (TM = Ni, Pd, and Pt) using B3LYP, CAM-B3LYP, M06-2X level of theories with the basis sets 6-31G*, 6-311G**, LANL2DZ, and SDD. The NBO analysis confirms the π bonding contribution is lesser than that of σ (sigma) bonding contribution in TM–InX bond and it emphasizes the greater contribution by the indium atom. The orbital interactions occur between indium and the transition metal (TM) via σ donation TM ← InX. The WBI analysis acknowledges that the TM = InX bonds are stronger than the TM–CO bonds. The energy gap between the HOMO–LUMO is predicted by FMO analysis. The EDA analysis confirms that the ΔEelstat (electrostatic interaction) is more than that of ΔEorb (covalent bonding) of the complexes. Graphic abstract
Keywords Indium monohalides · EDA · WBI · NBO · DFT (density functional theory) Electronic supplementary material The online version of this article (https://doi.org/10.1007/s11696-020-01297-w) contains supplementary material, which is available to authorized users. Extended author information available on the last page of the article
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Introduction The coordination of transition metal (TM) complexes with low valent group 13 diyl ligands ER (E = B–Tl) represent a synthetically challenging topic of comprehensive research that has accomplished major growth and led to the fruitful synthesis of different varieties of attractive complexes (Ln–TM–ER) (Macdonald and Cowley 1999; Braunschweig et al. 2006; Baker and Jones 2005; Aldridge and Coombs 2004; Paularokiadoss et al. 2020). As the result of the existence of the “lone-pair’’ of electrons in the E I ligands (Jutzi et al. 1999), the group 13 elements in complexes have + 1 oxidation state (EI) could act as Lewis acids or Lewis bases. And they have been used as donors for transition metal to develop new types of materials (Fischer and Weiss 1999; Aldridge 2006). Numerous experimental works have been done on TM complexes with group-13 elements based ligand with boron, aluminium, gallium, and indium; because of the ligand EIR is an isolobal analogue with CO. The magnitude of σ-contribution and π-acceptance is dependent upon the nature of the transition metals, and also the group R involved in it (Gemel et al. 2004). Common synthetic routes to transition metals with the heavier group 13 elements are the replacement of poorly bonded ligands like CO by the ligands of the type ER (E = Al, Ga and In) as well as insertion reactions and salt elimination (Uhl 1993; Dohmeier et al. 1996). Importance in the transition metals’ (TM) coordination with indium ligands has been witnessed in the recent decades and continue to draw the attention o
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