Electronic Properties and Reactivity of an Isolable Phosphagermaheterocyclic Carbene

Ghereg, Dumitru; Ladeira, Sonia; Saffon, Nathalie; Escudié, J.

doi:10.1002/anie.201102500

Cited by 12 publications

(4 citation statements)

References 40 publications

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“…[20,37] Further characteristic signals are found in the 13 (2) pm is about 10 pm longer than in related compounds. [38] The lengthening and the nearly planar coordination of the Ge atom by three C atoms (ΣC-Ge-C = 354°) are indicative of a considerable ionic character of the Ge-O bond. [39] 9 features an essentially planar GeNAlC heterocycle (largest deviation from plane: 6 pm) with exocyclic C=N (2)], C1-O1 126.9(1) [126.…”

Section: Hydrogermylation Reactionsmentioning

confidence: 99%

Aluminium Functionalized Germanes: Intramolecular Activation of Ge–H Bonds, Formation of a Dihydrogen Bond and Facile Hydrogermylation of Unsaturated Substrates

et al. 2019

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A series of alkenylhydrogermanes, RR′(H)Ge‐C(AlR′′2)=C(H)‐tBu [4a, R = R′ = Mes, R′′ = tBu; 4b, R = R′ = Mes, R′′ = CH(SiMe3)2; 5a, R = R′′ = tBu, R′ = CH2CH2tBu; 5b, R = tBu, R′ = CH2CH2tBu, R′′ = CH(SiMe3)2], was synthesized by hydroalumination of the respective alkynylgermanes, RR′(H)Ge‐C≡C‐tBu 3, with R′′2Al–H [R′′ = tBu, CH(SiMe3)2]. In the solid state compound 5b showed a contact between Al and the Ge bound H atom (293 pm) which according to quantum chemical calculations results in Ge–H bond activation. In case of less bulky substituents on Al (5a, R′′ = tBu) a mixture of isomers was observed that reacted with Et2NH to yield the simple Lewis acid‐base adduct [(tBu)(tBuCH2CH2)(H)Ge‐C(AltBu2)=C(H)‐tBu](HNEt2) (6). 6 features a dihydrogen bond (Ge–H···H–N) as evident from typical downfield (N–H) and high‐field (Ge–H) shifts in the NMR spectrum, red shifts of νGe‐H and νN‐H in the IR spectrum, a short H···H contact (210 pm) in the solid state and a bond critical point between both H atoms. The presence of a hard Lewis‐acidic Al atom in geminal position to the Ge–H bond in 5a facilitates reactions with Ph2CO, OC4H8N‐C≡N and Ph–NCO under surprisingly mild conditions by hydrogermylation of the heteronuclear π‐bonds and formation of four‐membered Ge–O/N–Al–C (7, 9) or six‐membered Ge–N–C–O–Al–C (8) heterocycles. Reaction with Ph–C≡C–H afforded the cis‐addition product 10, in which the α‐C atom of the new alkenyl group showed a close contact [258.3(2) pm] to the Al atom.

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Section: Hydrogermylation Reactionsmentioning

confidence: 99%

Aluminium Functionalized Germanes: Intramolecular Activation of Ge–H Bonds, Formation of a Dihydrogen Bond and Facile Hydrogermylation of Unsaturated Substrates

et al. 2019

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“…Hahn and co-workers prepared a molecular square featuring four dicarbene linkers. 48 49 In the 13 C NMR spectrum the carbenic carbon was observed at d C 196.7 ppm ( 1 J RhC 34.9 Hz).…”

Section: Rhodium/iridium N-heterocyclic Carbene Complexesmentioning

confidence: 99%

Cobalt, rhodium and iridium

Smith

2012

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

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This chapter provides a selective review of the literature for 2011 on the chemistry of the Group 9 elements. HighlightsThe year 2011 has witnessed some remarkable work in the field of Co, Rh and Ir chemistry. Some notable highlights include wireless solar water splitting (Co), 30 nitrenium ion complexes of Rh(I), 39 cleavage of aliphatic C-F bonds at an Ir(I) centre 77 and catalytic dehydroaromatisation of n-alkanes using Ir complexes.

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“…81 Reaction of Tip( t Bu)GeQCQPMes* with Ph 2 CQCQO leads to the formation of the carbene 48 which is stable at temperatures below 0 1C. 82 Reaction with [Rh(CO) 2 Cl] 2 allowed for the complex of 48 to be isolated. The adduct with PMe 3 was also reported.…”

Section: Phosphorusmentioning

confidence: 99%