Reactions of cyclotrigermane and germylenes with carbonyl compounds: Cycloadducts and oligomers

Valentin, Bruno; Castel, Annie; Rivière, P.; Mauzac, M.; Onyszchuk, M.; Lebuis, Anne‐Marie

doi:10.1002/(sici)1098-1071(1999)10:2<125::aid-hc5>3.3.co;2-a

Cited by 8 publications

(12 citation statements)

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“…‐ O 2 ketyl, perhaps because of its limited solubility in common solvents. However, there is an example of a complex containing a coordinated neutral acen ligand, [TiCl 4 (acen)], and some dianionic binolate–acen 2− Ge IV complexes …”

Section: Resultsmentioning

confidence: 99%

Bulky Ytterbium Formamidinates Stabilise Complexes with Radical Ligands, and Related Samarium “Tetracyclone” Chemistry

Werner

Zhao

Best

et al. 2017

Chemistry A European J

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Divalent [Yb(DippForm) (thf) ] (n=2 (1 a), or 1 (1 b), DippForm=N,N'-bis(2,6-diisopropylphenyl)formamidinate) complexes were treated with the ketones: 9-fluorenone (fn), or 2,3,4,5-tetraphenylcyclopentadienone (tpc, tetracyclone), giving ketyl complexes: [Yb(DippForm) (fn -O)(thf)] (2), and [Yb(DippForm) (tpc -O)] (3), respectively (ketyl=a radical anion containing a C -O group. By contrast, when perfluorobenzophenone (pfb) was treated with either 1 a or 1 b, transitory ketyl formation was followed by rapid decomposition through a C-F activation pathway, giving [YbF(DippForm) (thf)] (4 a) and a highly unusual fluoride/oxide-bridged species: [Yb F O (DippForm) ] (4 b). The reduction of diketones: 3,5-di-tert-butyl-1,2-benzoquinone (tbbq), 9,10-phenanthrenequinone (phen), or 1,2-acenaphthenequinone (acen), was also examined giving ketyl complexes: [Yb(DippForm) (tbbq -O )] (5), [Yb(DippForm) (phen -O )] (6), and [Yb(DippForm) (acen -O )(thf)] (7). An unsolvated derivative of 7, namely [Yb(DippForm) (acen -O )] (8), was obtained from PhMe. All ketyl complexes had suitably elongated C -O bonds, were stable in both polar and non-polar solvents-an uncommon trait for rare-earth ketyl complexes-and, with the exception of 3, showed radical signals in ESR spectra. To investigate the reactivity of the tpc -O ketyl complex, 3 was treated with oxidants (CS , Se) and reducing agents (Mg , KH, or [SmI (thf) ]). Thus 3 was oxidised to tpc by Se. Treatment of 3 with KH led to a ligand exchange process giving an unusual diketyl species [Yb(DippForm)(tpc -O) (thf) ] (10), which has two cisoid tpc -O ligands in very close proximity. When treated with [SmI (thf) ], the tpc -O ketyl was further reduced to a dianion (1-oxido-2,3,4,5-tetraphenylcyclopentadianide ), ({C Ph }-O) by [SmI (thf) ], giving dimeric [{SmI({C Ph }-O)(thf) } ] (Sm11) and monomeric complexes [YbI(DippForm) (thf)] (11 b) and [YbI (DippForm)(thf) ] (11 c). Activated Sm metal reduced neutral tetracyclone to the dianion, ({C Ph }-O) , in THF, giving tetranuclear [{Sm ({C Ph }-O) (thf) } ] (Sm13). Treatment of Sm13 with iodine in situ provided access to [{SmI({C Ph }-O)(thf) } ] (Sm11), in good yield.

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Section: Resultsmentioning

confidence: 99%

Bulky Ytterbium Formamidinates Stabilise Complexes with Radical Ligands, and Related Samarium “Tetracyclone” Chemistry

Werner

Zhao

Best

et al. 2017

Chemistry A European J

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“…Surprisingly, although the addition of carbonyl compounds to digermenes 1 to give 2,3-digermoxetanes was one of the first reported reactions 2 of this class of compounds, there is only one theoretical 3 and no experimental studies of the mechanism of this addition. 4 In fact, with a few notable exceptions, 5,6 the mechanism of the addition of carbonyl compounds to any doubly bonded Ge derivative remains unexplored. In addition to the fundamental importance of such mechanistic studies in molecular digermene chemistry, the results of such investigations are also relevant in the study of the chemical modification of germanium surfaces, particularly the Ge(100)-2 × 1 surface which is believed to be composed of germanium dimers.…”

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Mechanistic Studies of the Addition of Carbonyl Compounds to Tetramesityldigermene

Samuel

Baines

2003

J. Am. Chem. Soc.

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The mechanism of the addition of carbonyl compounds to digermenes was investigated by examining the reaction between tetramesityldigermene and two mechanistic probes: trans-2-phenylcyclopropane carbaldehyde and trans,trans-2-methoxy-3-phenylcyclopropane carbaldehyde. In each reaction, two diastereomers of the formal [2+2] cycloadduct between the aldehyde and the digermene were obtained. These findings, together with the results of a recent theoretical study, indicate that the addition of carbonyl compounds to digermenes proceeds via a mechanism involving a zwitterionic intermediate.

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“…In the case of germanium, the photochemistry of the cyclotrigermane (Mes 2 Ge) 3 has been the most extensively studied and it has been shown that this compound is photochemically converted to a germylene Mes 2 Ge : and a digermene Mes 2 Ge=GeMes 2 . The chemistry of both of these photoproducts has been thoroughly investigated , , , , , . However, only a few investigations into the photochemistry of linear oligogermanes have been described.…”

Section: Introductionmentioning

confidence: 99%

“…The photochemistry of catenated group 14 compounds is of interest since this method can be used to convert one type of catenate to another and also can be used for the generation of reactive intermediates including silylenes, germylenes, stannylenes, and group 14 element centered radical species that can be trapped and characterized . In the case of germanium, the photochemistry of the cyclotrigermane (Mes 2 Ge) 3 has been the most extensively studied and it has been shown that this compound is photochemically converted to a germylene Mes 2 Ge : and a digermene Mes 2 Ge=GeMes 2 .…”

Section: Introductionmentioning

confidence: 99%

Photodecompostion of the Oligogermanes nBu3GeGePh2GenBu3 and nBu3GeGePh3: Identification of the Photoproducts by Spectroscopic and Spectrometric Methods

et al. 2016

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The oligogermane nBu 3 GeGePh 2 GenBu 3 was photolyzed using UV-C light in the presence of acetic acid as a trapping agent and the photoproducts were identified using 1 H NMR spectroscopy, gas chromatography/electron-impact mass spectrometry, and high resolution accurate mass mass spectrometry. The products identified were the germanes nBu 3 GeH, nBu 3 GeOAc, and Ph 2 Ge(H)OAc (OAc = C 2 H 3 O 2 ) and the diger- [a]

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Reactions of cyclotrigermane and germylenes with carbonyl compounds: Cycloadducts and oligomers

Cited by 8 publications

References 0 publications

Bulky Ytterbium Formamidinates Stabilise Complexes with Radical Ligands, and Related Samarium “Tetracyclone” Chemistry

Bulky Ytterbium Formamidinates Stabilise Complexes with Radical Ligands, and Related Samarium “Tetracyclone” Chemistry

Mechanistic Studies of the Addition of Carbonyl Compounds to Tetramesityldigermene

Photodecompostion of the Oligogermanes nBu3GeGePh2GenBu3 and nBu3GeGePh3: Identification of the Photoproducts by Spectroscopic and Spectrometric Methods

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