The First Zwitterionic Dinuclear Germanium(IV) Complex with Pentacoordinate Germanium Atoms:  Synthesis and Crystal Structure Analysis

Tacke, Reinhold; Heermann, Joachim; Pfrommer, Brigitte

doi:10.1021/ic9713994

Cited by 6 publications

(6 citation statements)

References 14 publications

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“…In 1 there are four types of hydrogen bonding: (1) between the hydroxyl oxygen atom of coordinated HIBA and the oxygen atom of disordered nitrate (O···O, 2.739 and 2.762 Å), (2) between the hydroxyl oxygen atom of coordinated HIBA and the oxygen atom of disordered lattice water (O···O, 2.733 and 2.742 Å), (3) between the oxygen atom of coordinated water and the oxygen atom of the disordered nitrate (O···O, 2.722 Å), and (4) between the oxygen atom of coordinated water and the oxygen atom of lattice water (O···O, 2.660 Å). The O···O distances are in the usual range for complexes with HIBA ligands. − The two-dimensional sheets of the cationic units in 1 are linked together by hydrogen bonds to form a three-dimensional network with the nitrate anions arranged alternatively between the two-dimensional sheets. In Figure , the disordered nitrate anion lies between the first two layers and is only shown at one occupancy position, while the other 50% occupancy position is represented by a disordered water molecule (red balls).…”

Section: Resultsmentioning

confidence: 99%

“…Only a few crystal structures have been reported in the literature for HIBA–metal ion complexes. Carballo et al reported the structures of HIBA complexes with dioxovanadate(V), germanium(IV), copper(II), cobalt(II), manganese(II), and zinc(II). , In all of these complexes, HIBA acts as a monoanionic (O,O′)-bidentate ligand that chelates the metal cations through both carboxyl and hydroxyl groups (Scheme e). Despite the fact that HIBA has been used in lanthanide separations for over 55 years, there is only one reported crystal structure of a lanthanide with HIBA, La(HIBA) 2 ·Cl·2H 2 O .…”

Section: Introductionmentioning

confidence: 99%

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Solid-State and Solution-State Coordination Chemistry of Lanthanide(III) Complexes with α-Hydroxyisobutyric Acid

et al. 2012

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Despite the wide range of applications of α-hydroxyisobutyric acid (HIBA) in biochemical processes, pharmaceutical formulations, and group and elemental separations of lanthanides and actinides, the structures and geometries of lanthanide-HIBA complexes are still not well understood. We reacted HIBA with lanthanides in aqueous solution at pH = 5 and synthesized 14 lanthanide-HIBA complexes of the formula [Ln(HIBA)(2)(H(2)O)(2)](NO(3))·H(2)O (Ln = La (1), Ce (2), Pr (3), Nd (4), Sm (5), Eu (6), Gd (7), Tb (8), Dy (9), Ho (10), Er (11), Tm (12), Yb (13), Lu (14)), isolating single crystals (1-7, 10, and 11) and powders (8, 9, and 12-14). Both single-crystal and powder X-ray diffraction studies reveal a two-dimensional extended structure across the entire lanthanide series. The environment around the eight-coordinated Ln(III) atom is best described as a distorted dodecahedron, where HIBA acts as a monoanionic tridentate ligand with one carboxylato oxygen atom and one hydroxyl oxygen atom chelating to one Ln(III) center. The carboxylato oxygen atom from a second HIBA ligand bridges to a neighboring Ln(III) atom to form a two-dimensional extended structure. While the coordination mode for HIBA is identical across the lanthanide series, three different structure types are found for La, Ce-Ho, and Er-Lu. Solution characterization using (13)C NMR further confirmed a single solution complex under the crystallization conditions. Raman and UV-vis-NIR absorbance and diffuse reflectance spectra of HIBA-Ln(III) complexes were also measured.

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Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Solid-State and Solution-State Coordination Chemistry of Lanthanide(III) Complexes with α-Hydroxyisobutyric Acid

et al. 2012

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“…We report here the synthesis and crystal structure of dianionic compounds with a bond between pentacoordinated germanium atoms, digerma-nates. 9,10 We also describe their interconversion into the anionic and neutral Ge−Ge-bonded compounds to demonstrate the reactivities of the pentacoordinated Ge−Ge-bonded compounds.…”

Section: ■ Introductionmentioning

confidence: 71%

“…” Indeed, a Ge–Ge bond including one or two pentacoordinated atoms has been found only in a limited number of neutral compounds using an atrane framework or trichloroacetate or triflate ligands that bridge two germanium atoms (Chart ). We report here the synthesis and crystal structure of dianionic compounds with a bond between pentacoordinated germanium atoms, digermanates. , We also describe their interconversion into the anionic and neutral Ge–Ge-bonded compounds to demonstrate the reactivities of the pentacoordinated Ge–Ge-bonded compounds.…”

Section: Introductionmentioning

confidence: 99%

Interconversion among Dianionic, Anionic, and Neutral Compounds Bearing a Bond between Two Pentacoordinated Germanium Atoms

et al. 2014

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The first dianionic compounds bearing a bond between two pentacoordinated germanium atoms have been synthesized in a stable form as candidates for a core unit to construct unprecedented structures in group 14 element chemistry. X-ray crystallographic analysis and computational study indicated the single-bond character of the Ge–Ge bond. They were reversibly converted to the anionic and neutral Ge–Ge-bonded compounds while maintaining the coordination number of the germanium atoms. The interconversion features changes in structures around the germanium atoms, including changes from a staggered conformation of the Ge–O bonds to a parallel conformation.

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“…The geometry at each is found to be distorted tbp by crystallography. 125 The interaction of Lawesson's reagent (L.R.) with Ge[(NPr i CH) 2 ] gives 69, comprising a tetrahedral germanium, whereas Ge[{N(SiMe 3 ) 2 }] 2 gives 70 (Scheme 19).…”

Section: Scheme 16mentioning

confidence: 99%

5 Carbon, silicon, germanium, tin and lead

Parr

2000

Annu. Rep. Prog. Chem., Sect. A

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A number of review articles relevant to this chapter have appeared. The area of carbon-rich ligands has been the subject of two timely publications, a special issue of the Journal of Organometallic Chemistry 1 on carbon-rich organometallic complexes and a complementary review on cumulenylidenes. 2 The catalytic applications of metal vinylidenes 3 and the occurrence of planar carbon in organometallic complexes of group 4 and 5 elements 4 have also been reviewed. For silicon, reviews have been in the area of the formation of monolayers 5 and the chemical processing of silicon wafers. 6 A review discussing the role of p-block elements, largely tin, in determining the structure of heterometallic complexes has been published. 7 Despite the discovery of fullerenes, the newest allotrope of carbon, much interest remains in one of the older examples, diamond. The reaction of carbon tetrachloride with four equivalents of sodium metal at 973 K in the presence of a Co/Ni catalyst yields C dia . The product, identi¢ed by Raman spectroscopy, is formed as a powder in a low (ca. 2%) yield, but nevertheless this is amongst the lowest energy routes to industrial diamonds yet known. 8 The same product can be prepared using conditions designed to mimic those found on Uranus and Neptune in which methane is heated to (2^3) Â 10 3 K at pressures of 10^50 gigapascals, whereupon the methane breaks down to form diamond and polymeric hydrocarbons. 9 A convincing argument has been presented for the formation of such a dense solid from a light gaseous phase contributing to the internal heat, magnetic ¢eld and luminosity of a celestial body, and hence the possible signi¢cance of this process in planet formation. A report of the synthesis and identi¢cation of C 6 CH 2 as :C( C C) 2 C CH 2 by removal of the charge from the C 6 CH 2 À. radical anion during neutralisationreionisation mass spectroscopy has been published and related to the cumulenes found in circumstellar dust. 10 Cumulene complexes of transition metals continue to attract much attention. Although synthetic protocols are well established, some new approaches have appeared outlined in Scheme 1. 11,12 The last compound shown is a very rare example of a linear ten atom chain C 8 Rh 2 . Cumulenes with extremely long carbon chains have also appeared, such as 3 which shows in the solid state a distinct twisting of the C 12 chain away from linear, 13 and 4 and 5 (Scheme 2). The crystal structure of 5 shows C^C bond lengths of 1.210^1.233 Ð for triple bonds

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The First Zwitterionic Dinuclear Germanium(IV) Complex with Pentacoordinate Germanium Atoms: Synthesis and Crystal Structure Analysis

Cited by 6 publications

References 14 publications

Solid-State and Solution-State Coordination Chemistry of Lanthanide(III) Complexes with α-Hydroxyisobutyric Acid

Solid-State and Solution-State Coordination Chemistry of Lanthanide(III) Complexes with α-Hydroxyisobutyric Acid

Interconversion among Dianionic, Anionic, and Neutral Compounds Bearing a Bond between Two Pentacoordinated Germanium Atoms

5 Carbon, silicon, germanium, tin and lead

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