Characterization and X-ray crystal structure of a monomeric germylene derivative, Ge(acac)I (hacac = acetylacetone)

Stobart, Stephen R.; Hollander, Frederick J.; Youngs, Wiley J.

doi:10.1039/c39790000911

Cited by 22 publications

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“…The Ge–N bond lengths in germylene 2b have an average value of 1.964(2) Å and the shorter Ge–N bond length [1.856(3) Å] in 5b is a result of the higher oxidation state of germanium in this complex. The Ge–C bond length in 5b is 1.940(3) Å and is typical of a Ge–C single bond, and the Ge–I bond length of 2.7599(5) Å is similar to the Ge–I bond length in (acac)GeI [acac = acetylacetonato; 2.7360(3) Å] 18. However, the Ge–I bond in 5b is longer than the usual Ge–I bond length 17b.…”

Section: Results and Discussion Germylene Synthesismentioning

confidence: 94%

Stabilized Germylenes Based on Diethylenetriamines and Related Diamines: Synthesis, Structures, and Chemical Properties

et al. 2012

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A series of novel, low‐valent germanium compounds 2a–2j based on four diethylenetriamines 1a–1d, (methyl)bis(pyrrol‐2‐ylmethyl)amine (1e), N,N′‐(sulfanediyldibenzene‐2,1‐diyl)bis(pentafluoroaniline) (1f), N,N′‐(oxydibenzene‐2,1‐diyl)bis(pentafluoroaniline) (1g), and (pentafluorophenyl)amines 1i and 1j have been obtained either by the reaction of Ge[N(SiMe3)2]2 with various diamines (1a–1e) or by the metathesis reaction of [GeCl2·dioxane] with lithium amides. The oxidative insertion (with halogenation reagents, MeI, disulfides), [1+4] cycloaddition, and oxidation reactions of the synthesized germylenes were investigated. The compositions and structures of the novel compounds were established by elemental analysis, 1H and 13C NMR spectroscopy, and X‐ray diffraction analysis (germylenes 2b, 2i, 2j, Ge4+ compounds 5b, 7a, 7b, 8, 10, 11). All the synthesized germylenes are monomeric.

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Section: Results and Discussion Germylene Synthesismentioning

confidence: 94%

Stabilized Germylenes Based on Diethylenetriamines and Related Diamines: Synthesis, Structures, and Chemical Properties

et al. 2012

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“…Calculations indicate that the β-diketiminatogermanium(II) and tin(II) are strong σ -donors that possess low π -acceptor properties toward the (13), N(1)-Ge-Cl 95.41 (9), N(2)-Ge-Cl 93.41 (9), N(1)-Ge-W. 126.14 (9), N(2)-Ge-W 125.57(9), Cl-Ge-W 115.15(3).…”

Section: Resultsmentioning

confidence: 99%

“…Two 13 C NMR resonances for the CO groups and three bands in the IR spectra are characteristic of the local symmetries around the tungsten (C 4v ).…”

Section: (4)mentioning

confidence: 99%

Three‐coordinate divalent Group 14 element derivatives and related compounds

Saur

Alonso

Barrau

2005

Applied Organom Chemis

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INTRODUCTIONThis paper is an overview of a particular part of our systematic investigation of the divalent germanium and tin species focusing on the use in this chemistry of a β-diketiminato ligand with no encumbering aryl groups on the nitrogen. The bidentate three-atom bridging ligand L 2 (L 2 = PhNC(Me)CHC(Me)NPh), by its remarkable stabilizing properties, allows for easy isolation of subvalent germanium and tin compounds and, as such, permits a general insight on the chemistry of such species. The emphasis here will be on the divalent species L 2 (X)M (M = Ge, Sn), the germanechalcogenones L 2 (Cl)Ge Y, the transition- L (n−x) and the cationic ger- IntroductionThe divalent species of Group 14 elements are the heavier carbene analogues; for recent reviews, see Refs 6-10. They are generally transient species. As a general rule, when these species contain unfunctionalized organic ligands, they undergo rapid oligomerization and polymerization. In the last two decades, two principal methods of stabilization have been particularly investigated. Thus, various kinetically and/or thermodynamically stabilized divalent germanium and tin compounds have been isolated in a monomeric state. 1 -5,11 -81 The use of bulky groups bound to the Group 14 element to prevent aggregation permitted the first syntheses of stable monomer divalent species; the most noticeable are the dialkyl-germylene and -stannylene reported by Lappert and co-workers, 12 the first stable monomeric arylgermylene ((Mes * ) 2 Ge (Mes * = 2,4,6-t Bu 3 -phenyl)) described by Du Mont and co-workers, 14 and the well-known aryl-germylene and -stannylene Tbt(Tip)M 14 (M 14 = Ge, Sn; Tbt = 2,4,6-tris[bis(trimethylsilyl)methyl]phenyl, Tip = 2,4,6-i Pr 3 -phenyl) of Okazaki and co-workers. 25,29The ligand backbone may also play an important role in improving stability. Thus, the presence of ligands with donor side arms on the germanium or the tin element can (by transfer of electron density) reduce the deficit on 37 is, to our knowledge, the first example of an intramolecular base stabilized homoleptic dialkylgermylene. Various amino-, phosphino-, thioalkoxy-, alkoxy-and aryloxy-divalent species have also been isolated in monomeric form owing to this method of stabilization; one should mention in particular the studies of Jutzi and co-workers, 28,32,54,71 Veith and coworkers, 15,18,40,66 Parkin and co-workers, 67 Jurkschat and co-workers, 77,78 Dias and co-workers 31,35,42,69,80,81 and Roesky and co-workers. Main Group Metal Compounds -5Although a large number of homoleptic divalent germanium and tin species have been isolated using these concepts of stabilization, there are fewer examples of heteroleptic compounds having been reported, though the first functional heteroleptic germylenes R(Cl)Ge (R = Et, Ph) were obtained as viscous oils in the 1970 by our group.6 Few solidstate structures of such heteroleptic compounds have been described. Noteworthy examples are in the area of thermodynamic stabilization, the acetylacetonatogermylene R(I)Ge (R = OC (Me) 46...

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“…Only a few have been studied by X-ray analysis in a monomeric form: AcacGe-I (acac = acetylacetone) [10], Ge(OCH 2 CH 2 NMe 2 ) 2 [9g], Ge(OCH 2 CH 2 NMe 2 )Cl [9h], Ge(OCH 2 CH 2 NMe 2 )-OCOCH 3 [9h]; in all these structures a supplementary coordination of an oxygen or a nitrogen atom of the ligand to the germanium is evidenced in the solid state. In the case of non-coordinated germylenes, the structure of Ge-…”

Section: Resultsmentioning

confidence: 99%

Synthesis and chemistry of aryloxygermylene-amine complexes

Bonnefille

Mazières

Hawi

et al. 2006

Journal of Organometallic Chemistry

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Characterization and X-ray crystal structure of a monomeric germylene derivative, Ge(acac)I (hacac = acetylacetone)

Abstract: The complex Ge(acac) I (Hacac = acetylacetone) has been characterized and its structure determined by a single-crystal X-ray structural analysis ; the monomeric molecule is pyramidal with bond lengths Ge-I, 2.736(1)

Cited by 22 publications

References 0 publications

Stabilized Germylenes Based on Diethylenetriamines and Related Diamines: Synthesis, Structures, and Chemical Properties

Stabilized Germylenes Based on Diethylenetriamines and Related Diamines: Synthesis, Structures, and Chemical Properties

Three‐coordinate divalent Group 14 element derivatives and related compounds

Synthesis and chemistry of aryloxygermylene-amine complexes

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