Amidinate based indium(<scp>iii</scp>) monohalides and β-diketiminate stabilized In(<scp>ii</scp>)–In(<scp>ii</scp>) bond: synthesis, crystal structure, and computational study

Banerjee, Samya; Dutta, Sayan; Sarkar, Samir Kumar; Graw, Nico; Herbst‐Irmer, Regine; Koley, Debasis; Roesky, Herbert W.

doi:10.1039/d0dt03161e

Cited by 8 publications

(3 citation statements)

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“…indium(III)-seamed capsules,) and synthetic inorganic chemistry (e.g. compounds with In II –In II bonds). , Since indium-115 (nuclear spin I = 9/2, 95.72% natural abundance) is an NMR-active nucleus, 115 In NMR spectroscopy is emerging as a valuable solid-state technique to study In compounds. , In the present work we have employed this spectroscopic tool in combination with single-crystal crystallography but we also used this tool to characterize a complex with an unknown X-ray structure.…”

Section: Introductionmentioning

confidence: 99%

Indium(III) in the “Periodic Table” of Di(2-pyridyl) Ketone: An Unprecedented Transformation of the Ligand and Solid-State ¹¹⁵In NMR Spectroscopy as a Valuable Structural Tool

et al. 2021

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Reactions of di(2-pyridyl) ketone, (py) 2 CO, with indium-(III) halides in CH 3 NO 2 have been studied, and a new transformation of the ligand has been revealed. In the presence of In III , the CO bond of (py) 2 CO is subjected to nucleophilic attack by the carbanion − :CH 2 NO 2 , yielding the dinuclear complexes [In 2 X 4 {(py) 2 C(CH 2 NO 2 )(O)} 2 ] (X = Cl, 1; X = Br, 2; X = I, 3) in moderate to good yields. The alkoxo oxygens of the two η 1 :η 2 :η 1 -(py) 2 C(CH 2 NO 2 )(O) − ligands doubly bridge the In III centers and create a {In 2 (μ 2 -OR) 2 } 4+ core. Two pyridyl nitrogens of different organic ligands and two terminal halogeno ions complete a distorted-octahedral stereochemistry around each In(III) ion. After maximum excitation at 360 or 380 nm, the solid chloro complex 1 emits blue light at 420 and 440 nm at room temperature, the emission being attributed to charge transfer within the coordinated organic ligand. Solidstate 115 In NMR spectra, in combination with DFT calculations, of 1−3 have been studied in detail at both 9.4 and 14.1 T magnetic fields. The nuclear quadrupolar and chemical shift parameters provide valuable findings concerning the electric field gradients and magnetic shielding at the nuclei of indium, respectively. The experimentally derived C Q values are 40 ± 3 MHz for 1, 46 ± 5 MHz for 2, and 50 ± 10 and 64 ± 7 MHz for the two crystallographically independent In III sites for 3, while the δ iso values fall in the range 130 ± 30 to −290 ± 60 ppm. The calculated C Q and asymmetry parameter (η Q ) values are fully consistent with the experimental values for 1 and 2 and are in fairly good agreement for 3. The results have been analyzed and discussed in terms of the known (1, 3) and proposed (2) structural features of the complexes, demonstrating that 115 In NMR is an effective solid-state technique for the study of indium(III) complexes.

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Section: Introductionmentioning

confidence: 99%

Indium(III) in the “Periodic Table” of Di(2-pyridyl) Ketone: An Unprecedented Transformation of the Ligand and Solid-State ¹¹⁵In NMR Spectroscopy as a Valuable Structural Tool

et al. 2021

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“…In recent times, amidinates with the general formula [R 1 C-(NR) 2 ] À are widely used to develop compounds from f-group metals to main group elements such as silicon, [1][2][3][4][5][6][7][8][9][10] germanium, [9,11] strontium, [12] calcium, [13] magnesium, [14] tin, [15] gallium, [16][17][18] indium [19][20][21][22] etc. This class of ligands is easy to synthesize and known to increase the stability of the resulting compounds.…”

Section: Introductionmentioning

confidence: 99%

Preparation and Reactivity Studies of Four and Five coordinated Amidinate Aluminum Compounds

Banerjee

Kumar

Bose

et al. 2021

Zeitschrift anorg allge chemie

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Synthesis of four and five coordinated aluminum amidinate (PhC(N t Bu) 2 =L) compounds are reported herein along with their single-crystal X-ray structures and detailed characterizations using both, experimental and computational techniques. LAlCl 2 (1) and L 2 AlCl (2) were synthesized by treating AlCl 3 with PhC (N t Bu) 2 Li in an equivalent ratio of 1 : 1 and 1 : 2, respectively. [LAl (C 2 H 5 )Cl] (3) was prepared from a reaction of AlCl 2 (C 2 H 5 ) with PhC(N t Bu) 2 Li in an equivalent ratio of 1 : 1. Reactivity of 3, an amidinate based organo-aluminum compound is explored for the various reactions. 3 produced [LAl(C 2 H 5 )(μ-F)] 2 (4) on treatment with Me 3 SnF. Interestingly, [LAl(C 2 H 5 )Cl] (3) was converted to [LAlCl(μ-OEt)] 2 (5) when refluxed in Et 2 O. 3 gives the monomeric and neutral cyclic (alkyl)(amino) carbene (cAAC) based radical [LAl(C 2 H 5 )(cAAC)] ( 6) on reduction with KC 8 in the presence of cAAC.

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“…The In-Br (2.5355(4) Å) bond lengths in 3 are in line with literature-known bromidoindinates In-Br (2.5541(4)-2.5615(4) Å) 38 . The In-N (average 2.240(3) Å) are in the range of pentacoordinated indium centres, for example, (bis)amidinate indiumbromide (2.1727(18)-2.2503(19) Å) 39 . Each indiumbromide-calix [4]pyrrolate can be understood as dianionic, rendering the four-membered Bi ring formally tetracationic, with a formal oxidation state of each Bi atom as +1.…”

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Supramolecular trapping of a cationic all-metal σ-aromatic {Bi4} ring

Yadav,

Maiti,

Schorpp

et al. 2024

Nat. Chem.

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Aromaticity in organic molecules is well defined, but its role in metal-only rings remains controversial. Here we introduce a supramolecular stabilization approach of a cationic {Bi4} rhomboid within the symmetric charge sphere of two bowl-shaped dianionic calix[4]pyrrolato indinates. Crystallographic and spectroscopic characterization, quantum chemical analysis and magnetically induced ring currents indicate σ-aromaticity in the formally tetracationic 16-valence electron [Bi4]4+ ring. Computational screening for other p-block elements identifies the planar rhomboid as the globally preferred structure for 16-valence electron four-atomic clusters. The aromatic [Bi4]4+ is isoelectronic to the [Al4]4−, a motif previously observed as antiaromatic in Li3[Al4]− in the gas phase. Thus, subtle factors such as charge isotropy seem to decide over aromaticity or antiaromaticity, advising for caution in debates based on the Hückel model—a concept valid for second-row elements but less deterministic for the heavier congeners.

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Amidinate based indium(iii) monohalides and β-diketiminate stabilized In(ii)–In(ii) bond: synthesis, crystal structure, and computational study

Abstract: In recent years, amidinates, the NCN-analogues of the allylic group have attracted attention as ligands for main group elements.1-4 The importance of the amidinate/s supported compounds of group 13 elements...

Cited by 8 publications

References 41 publications

Indium(III) in the “Periodic Table” of Di(2-pyridyl) Ketone: An Unprecedented Transformation of the Ligand and Solid-State ¹¹⁵In NMR Spectroscopy as a Valuable Structural Tool

Indium(III) in the “Periodic Table” of Di(2-pyridyl) Ketone: An Unprecedented Transformation of the Ligand and Solid-State ¹¹⁵In NMR Spectroscopy as a Valuable Structural Tool

Preparation and Reactivity Studies of Four and Five coordinated Amidinate Aluminum Compounds

Supramolecular trapping of a cationic all-metal σ-aromatic {Bi4} ring

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Amidinate based indium(iii) monohalides and β-diketiminate stabilized In(ii)–In(ii) bond: synthesis, crystal structure, and computational study

Abstract: In recent years, amidinates, the NCN-analogues of the allylic group have attracted attention as ligands for main group elements.1-4 The importance of the amidinate/s supported compounds of group 13 elements...

Cited by 8 publications

References 41 publications

Indium(III) in the “Periodic Table” of Di(2-pyridyl) Ketone: An Unprecedented Transformation of the Ligand and Solid-State 115In NMR Spectroscopy as a Valuable Structural Tool

Indium(III) in the “Periodic Table” of Di(2-pyridyl) Ketone: An Unprecedented Transformation of the Ligand and Solid-State 115In NMR Spectroscopy as a Valuable Structural Tool

Preparation and Reactivity Studies of Four and Five coordinated Amidinate Aluminum Compounds

Supramolecular trapping of a cationic all-metal σ-aromatic {Bi4} ring

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Indium(III) in the “Periodic Table” of Di(2-pyridyl) Ketone: An Unprecedented Transformation of the Ligand and Solid-State ¹¹⁵In NMR Spectroscopy as a Valuable Structural Tool

Indium(III) in the “Periodic Table” of Di(2-pyridyl) Ketone: An Unprecedented Transformation of the Ligand and Solid-State ¹¹⁵In NMR Spectroscopy as a Valuable Structural Tool