Stabilized germylenes based on dialkanolamines: Synthesis, structure, chemical properties

Huang, Miaoliang; Kireenko, Marina M.; Zaitsev, Kirill V.; Oprunenko, Yuri F.; Churakov, Andrei V.; Howard, Judith A. K.; Zabalov, M. V.; Lermontova, Elmira Kh.; Linder, Thomas; Karlov, Sergey S.; Зайцева, Г. С.

doi:10.1016/j.jorganchem.2012.01.018

Cited by 27 publications

(17 citation statements)

References 83 publications

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“…This can be attributed to the greater strength of the S–S bond in diethyl disulfide compared than in diphenyl disulfide. The relative reactivities of the germylenes based on diethylenetriamines with disulfides are similar to those found earlier for germanium(II) dialkanolamine derivatives 6…”

Section: Results and Discussion Germylene Synthesissupporting

confidence: 86%

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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 Synthesissupporting

confidence: 86%

“…Germylenes 2f – j based on a set of novel chelating bis(diarylamido) ligands were prepared for comparison. This work forms a part of our studies on the synthesis and investigation of “heavy carbene” analogues stabilized by polydentate ligands 6…”

Section: Introductionmentioning

confidence: 99%

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

et al. 2012

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“…The compounds 1 , 2 , R a ‐ 3 and S a ‐ 3 are monomeric in the solid state and show a distorted tetrahedral coordination at their germanium atom. The Ge‐S benzylic bond lengths (2.1836(5) Å and 2.1969(5) Å for 1 ; 2.157(2) Å and 2.164(2) Å for R a ‐ 3 ; 2.167(2) Å and 2.1707(19) Å for S a ‐ 3 ) and the Ge‐S benzenethiolate distances (2.2292(5) Å and 2.2270(5) Å for 1 ; 2.1910(7) Å and 2.1956(7) Å for 2 ) are in agreement with values reported for the structurally related 2,2’‐spirobi[benzo[ d ][1,3,2]dithiagermole] (Ge−S 2.195(2) – 2.199(2) Å) and other germanium thiolates exhibiting tetrahedral coordination of the germanium atom such as tetrakis(phenylthio)germane (Ge−S 2.2149(6) – 2.2191(5) Å) and tetrakis( p ‐tolylthio)germane (Ge−S 2.211(1) – 2.221(1) Å) . The Ge‐O benzylic bond lengths of thiolate 2 (1.744(2) Å and 1.7657(19) Å) and the Ge‐O phenolate distances of R a ‐ 3 (1.767(5) Å and 1.775(5) Å) and S a ‐ 3 (1.783(4) Å and 1.784(4) Å) are slightly shorter than the values reported for 6‐bromo‐2,2‐di‐ tert ‐butyl‐4 H ‐1,3,2‐benzo[ d ]dioxagermine (Ge‐O benzylic 1.7846(18) Å and Ge‐O phenolate 1.8168(17) Å) .…”

Section: Resultsmentioning

confidence: 99%

Chiral Spirocyclic Germanium Thiolates - An Evaluation of Their Suitability for Twin Polymerization based on A Combined Experimental and Theoretical Study

et al. 2016

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The spirocyclic germanium thiolates, 4H,4’H‐2,2’‐spirobi[benzo[d][1,3,2]dithiagermine] (1), 4H,4’H‐2,2’‐spirobi[benzo[d][1,3,2]oxathiagermine] (2) and 4H,4’H‐2,2’‐spirobi[benzo[e][1,3,2]oxathiagermine] (3) were synthesized and fully characterized. Compound 3 crystallizes as racemic conglomerate, whereas 1 and 2 give racemates in the solid state. Their reactivity towards twin polymerization (TP) was tested. The studies with regard to proton‐assisted TP revealed a significantly reduced reactivity as compared to the recently reported silicon derivative, 4H,4’H‐2,2’‐spirobi[benzo[d][1,3,2]dioxasiline] (A). DFT−D calculations were performed for 1–3 and the model compound 4H,4’H‐2,2’‐spirobi[benzo[d][1,3,2]dioxagermine] (4) to evaluate the first reaction step initiating the processes of proton‐assisted TP. Compound 4 with germanium bound to four oxygen atoms proved to be the most reactive precursor, but its synthesis failed. As indicated by the DFT−D calculations, compounds 1 and 2 are not suitable for TP. Starting from compound 3 a germanium and sulfur containing organic‐inorganic hybrid material was obtained by thermal annealing.

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“…However, the additional coordination does not significantly influence the bond lengths in the Ge 2 O 2 ‐ring in relation to those in E – G . Compound 1 is the first example of an alkoxygermylene exhibiting additional intramolecular coordination by an oxygen donor, whereas additional intramolecular coordination by nitrogen donors has recently been reported for alkoxygermylenes based on dialkanolamides10 and ( Z )‐2‐(pyridin‐2‐yl)ethenolates 7f. The Ge–O terminal distances in ( 1 ) 2 are 1.799(4) Å, whereas the Ge–O bridging bond lengths are significantly longer [Ge1–O1 1.957(3) Å and Ge1–O1′ 2.020(3) Å].…”

Section: Resultsmentioning

confidence: 99%

From a Germylene to an “Inorganic Adamantane”: [{Ge₄(μ‐O)₂(μ‐OH)₄}{W(CO)₅}₄]·4THF

et al. 2015

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Keywords: Germylenes / Germanium / Cluster compounds / Inorganic adamantanes / Density functional calculationsGermanium(II)(2-methoxyphenyl)methoxide(1)and[W(CO) 5 -(thf)] gave rise reproducibly (79 % yield) to a new, uncharged transition-metal complex of a germanium(II) hydroxido oxido cluster -[{Ge 4 (μ-O) 2 (μ-OH) 4 }{W(CO) 5 } 4 ]·4THF (2·4THF) -as a product of hydrolysis. The germylene 1 is monomeric in solution at ambient temperature but forms dimers in solution at low temperatures and in the solid state. Dimerization of compound 1 was studied by 1 H NMR spectroscopy and with [a] Technische Universität Chemnitz, 4996 the aid of DFT-D calculations. The tetranuclear cluster 2shows an adamantane-like core structure with coordination of tungsten pentacarbonyl to germanium(II) in the solid state as well as in solution. Characterization of both compounds, including by single-crystal X-ray diffraction analysis, by 1 H NMR, 13 C{ 1 H} NMR, FTIR spectroscopy, and through thermal analyses, is presented.

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Stabilized germylenes based on dialkanolamines: Synthesis, structure, chemical properties

Cited by 27 publications

References 83 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

Chiral Spirocyclic Germanium Thiolates - An Evaluation of Their Suitability for Twin Polymerization based on A Combined Experimental and Theoretical Study

From a Germylene to an “Inorganic Adamantane”: [{Ge₄(μ‐O)₂(μ‐OH)₄}{W(CO)₅}₄]·4THF

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Stabilized germylenes based on dialkanolamines: Synthesis, structure, chemical properties

Cited by 27 publications

References 83 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

Chiral Spirocyclic Germanium Thiolates - An Evaluation of Their Suitability for Twin Polymerization based on A Combined Experimental and Theoretical Study

From a Germylene to an “Inorganic Adamantane”: [{Ge4(μ‐O)2(μ‐OH)4}{W(CO)5}4]·4THF

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From a Germylene to an “Inorganic Adamantane”: [{Ge₄(μ‐O)₂(μ‐OH)₄}{W(CO)₅}₄]·4THF