Synthesis, characterization, and decomposition of the first mononuclear eight-coordinate indium(III) benzoate, In(.eta.2-O2CC6H5)3(4-Mepy)2

Andras, Maria T.; Hepp, Aloysius F.; Duraj, Stan A.; Clark, Eric; Scheiman, Daniel A.; Fanwick, Phillip E.; Hehemann, David G.

doi:10.1021/ic00071a030

Cited by 18 publications

(6 citation statements)

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“…Indium(III) centered MOFs have become an attractive target due to the ability of In(III) to bind up to six X-type ligands to attain an overall negative three formal charge, , allowing for the synthesis of charge neutral, anionic, and cationic frameworks. This diversity in coordination chemistry of In(III) centers offers the potential for the synthesis of equally diverse In-centered MOFs. − Traditionally, In-derived MOFs adopt one of three “standard” SBUs: monomeric [In(O 2 CR) 4 ] − , − infinite chain [In(μ-O 2 CR) 2 (μ-OH)] ∞ , − and trimeric {In 3 O(O 2 CR) 6 (H 2 O) 3 ] + (Figure ). − Although other In-derived SBU’s have been reported, − the full gamut of In coordination chemistry has yet to be realized in MOF architectures, especially with nodes possessing a formal anionic charge.…”

Section: Introductionmentioning

confidence: 99%

Ion-Directed Synthesis of Indium-Derived 2,5-Thiophenedicarboxylate Metal–Organic Frameworks: Tuning Framework Dimensionality

Mihaly

Zeller

Genna

2016

Crystal Growth & Design

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Template directed synthesis of metal–organic frameworks (MOFs) is of increasing interest. Herein we report the synthesis of six new MOFs synthesized from 2,5-thiophenedicarboxylic acid (TDC) and InCl3. The new frameworks are formally two- (YCM-21) and one-dimensional (YCM-22) anionic, as well as three-dimensional neutral (YCM-23). YCM-22 contains an unprecedented dianionic [InCl3(κ2-O2CAr)2]2– node. The structural diversity represented by these materials is entirely controlled by addition of organic ammonium salts during the synthesis process. The role of the additives is briefly discussed with observed correlations of (1) hydrogen bonding and cation−π interactions influencing MOF dimensionality and (2) the presence of anionic chlorides creating a chlorine-rich metal center leading to a one-dimensional framework.

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Section: Introductionmentioning

confidence: 99%

Ion-Directed Synthesis of Indium-Derived 2,5-Thiophenedicarboxylate Metal–Organic Frameworks: Tuning Framework Dimensionality

Mihaly

Zeller

Genna

2016

Crystal Growth & Design

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“…The ln-0 bond lengths are only slightly shorter than those reported for the eight-coordinate complex Ιη(ΟΗ 3 000) 3 .ί (both for L = bipy and phen In-O = 2.30 A), 16 whereas the In-N distances are significantly longer than the values found in these compounds (2.32 and 2.34 A for the bipy and phen species, respectively) and in a further eight-coordinate complex of Ιη(η -02CCgH5)3(4-Mepy)2 (2.34 A). 17 Therefore, such a difference in In-N and In-O bond lengths cannot be attributed only to strong binding between negatively charged carboxylate oxygen and ln 3+ , but rather to the geometric requirements of the tripodal structure of the nta 3 " ligand. The last assumption may be confirmed indirectly by comparison of a nitrilotriacetate anion with tripodal amine phenol ligands.…”

Section: Resultsmentioning

confidence: 99%

Seven- And Eight-Coordinate Complexes of Indium(iii) With Nitrilotriacetate

Malyarick¹,

Ilyuhin²,

Petrosyants³

1994

Main Group Metal Chemistry

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The crystal structures of three indium(lll) complexes with nitrilotriacetate (nta) have been determined. Crystallographic data for the compounds are as follows: [ln(nta)(H20)2] n .2nH20(1), orthorombic, space group P2 1 2 1 2 1 , a = 7.870(1), b = 11.505(2), c = 13.721(3) A, V = 1242.4(4) A 3 and Ζ = 4; Κ 3 [Ιη(ηί3) 2 ].5Η2θ (2), monoclinic, space groupP2i/c, a = 15.599(4), b = 9.814(2), c = 16.057(4) Α, β = 110.00(2)°, V = 2310(1) A 3 and Ζ = 4; {C(NH 2 )3}3[ln(nta) 2 ].2H 2 0 (3), triclinic, space group ΡΪ a = 9.517(3), b = 9.717(2), c = 15.306(4) Α, α = 76.17(2), β = 89.47(2), γ = 88.75(2)°, V = 1374.1(6) A 3 and Ζ = 2. In the polymeric-chain structure of 1 the In atom is seven-coordinated by two water molecules and nta 3 ", the latter being quadridentate towards one indium and forming bridges between two metal centres, whereas compounds 2 and 3 have monomeric structure with eight-coordinate complex anions containing two quadridentate nta ligands. The coordination geometry around the In atom is: a trigonal prism capped on a square face (1), a nearly ideal dodecahedron (2) and a highly distorted tetragonal antiprism (3).

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“…We had previously exploited this chemistry when we prepared the first example of an eight-coordinate indium benzoate, In(O 2 CC 6 H 5 ) 3 (4-Mepy) 2 , by oxidation of indium metal powder with a 3:2 excess of benzoyl peroxide in γ-picoline (Ref. 10). The use of the indium (I) chloride starting material provides a site for further chemistry to be utilized for preparation of mixed-metal complexes or clusters (Refs.…”

Section: Synthesis Of Compounds 1 Andmentioning

confidence: 99%

Synthesis of two new group 13 benzoato–chloro complexes: A structural study of gallium and indium chelating carboxylates

Duraj

Hepp

Woloszynek

et al. 2011

Inorganica Chimica Acta

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Synthesis, characterization, and decomposition of the first mononuclear eight-coordinate indium(III) benzoate, In(.eta.2-O2CC6H5)3(4-Mepy)2

Cited by 18 publications

References 0 publications

Ion-Directed Synthesis of Indium-Derived 2,5-Thiophenedicarboxylate Metal–Organic Frameworks: Tuning Framework Dimensionality

Ion-Directed Synthesis of Indium-Derived 2,5-Thiophenedicarboxylate Metal–Organic Frameworks: Tuning Framework Dimensionality

Seven- And Eight-Coordinate Complexes of Indium(iii) With Nitrilotriacetate

Synthesis of two new group 13 benzoato–chloro complexes: A structural study of gallium and indium chelating carboxylates

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