Germylenes

Nakata, Norio

doi:10.1002/9781119613466.ch9

Cited by 4 publications

(1 citation statement)

References 188 publications

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“…Tetrylenes [3][4][5][6][7]-heavier carbene analogs-have recently attracted significant attention [8][9][10][11][12][13][14][15][16][17][18][19][20]), primarily due to their possible application as analogs of transition metals in catalysis [21][22][23], in activation of small molecules [24][25][26][27][28][29][30], as ligands [31,32], in possible synthesis of derivatives with E-E bonds [33][34][35], reagents for synthesis [36][37][38][39] or precursors [40][41][42] in material chemistry. These species are reactive and unstable; to stabilize them, the introduction of bulky groups (kinetic stabilization) or polydentate ligands (thermodynamic stabilization) is used.…”

Section: Introductionmentioning

confidence: 99%

Germanium Complexes with ONO Tridentate Ligands: O-H Bond Activation Control According to DFT Calculations

Zaitsev

Trubachev

Полещук

2023

IJMS

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Polydentate ligands are used for thermodynamic stabilization of tetrylenes—low-valent derivatives of Group 14 elements (E = Si, Ge, Sn, Pb). This work shows by DFT calculations how the structure (the presence or absence of substituents) and type (alcoholic, Alk, or phenolic, Ar) of tridentate ligands 2,6-pyridinobis(1,2-ethanols) [AlkONOR]H2 and 2,6-pyridinobis(1,2-phenols) [ArONOR]H2 (R = H, Me) may affect the reactivity or stabilization of tetrylene, indicating the unprecedented behavior of Main Group elements. This enables the unique control of the type of the occurring reaction. We found that unhindered [ONOH]H2 ligands predominantly led to hypercoordinated bis-liganded {[ONOH]}2Ge complexes, where an E(+2) intermediate was inserted into the ArO-H bond with subsequent H2 evolution. In contrast, substituted [ONOMe]H2 ligands gave [ONOMe]Ge: germylenes, which may be regarded as kinetic stabilized products; their transformation into E(+4) species is also thermodynamically favorable. The latter reaction is more probable for phenolic [ArONO]H2 ligands than for alcoholic [AlkONO]H2. The thermodynamics and possible intermediates of the reactions were also investigated.

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Section: Introductionmentioning

confidence: 99%

Germanium Complexes with ONO Tridentate Ligands: O-H Bond Activation Control According to DFT Calculations

Zaitsev

Trubachev

Полещук

2023

IJMS

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Syntheses of Iminophosphomamido Chlorogermylenes and Their Complexation with a Rhodium(I) Complex

Takahashi,

Kamiyama,

Ishii

et al. 2023

Chemistry An Asian Journal

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Three‐coordinated chlorogermylenes of the type [Ph2P(RN)2]GeCl (3: R=tBu; 4: R=Dip=2,6‐iPr2C6H3), which bear an N,N‐substituted iminophosphonamide ligand, were synthesized. The coordination behavior of 3 and 4 toward rhodium(I) complex was investigated. When 3 was treated with 1/2 of an equivalent of [RhCl(cod)]2 (cod=1,5‐cyclooctadiene), the corresponding chlorogermylene‐Rh(I) complex 5 was obtained as orange crystals. In contrast, the reaction of 4 with a half equivalent of [RhCl(cod)]2 under a CO atmosphere resulted in the formation of a five‐membered germarhodacycle 7. Compounds 3, 4, 5, and 7 were characterized using NMR spectroscopies and single‐crystal X‐ray diffraction. Complex 5 can be employed as a catalyst for the hydrosilylation and hydroboration reactions of diphenylacetylene, thus demonstrating the utility of germylene ligands comparable to those of NHCs in the major transition metal catalytic processes.

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Electrophilic Behavior of the “Nucleophilic” Pyramidane: Reactivity of Ge‐Pyramidane towards Organolithium Reagents

Lee,

Wang,

Sasamori

et al. 2024

Chemistry A European J

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The particular reactivity of the recently discovered class of the main group element polyhedral clusters, pyramidanes, remains largely unexplored. In this communication, we report the reaction of the germapyramidane with tert‐butyllithium leading to the rather unusual organogermanium compound [Li+(thf)2]·2–, as the product of the formal insertion of a Ge‐apex into the C–Li bond. This reactivity mode exemplifies unusual electrophilic behaviour of a pyramidane, which is a priori considered as a nucleophilic reagent. Being highly reactive, [Li+(thf)2]·2– readily undergoes reactions with electrophiles (MeI, EtBr), initially forming intermediate germahousenes, which isomerize to the thermodynamically more favourable germoles.

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Germylenes

Cited by 4 publications

References 188 publications

Germanium Complexes with ONO Tridentate Ligands: O-H Bond Activation Control According to DFT Calculations

Germanium Complexes with ONO Tridentate Ligands: O-H Bond Activation Control According to DFT Calculations

Syntheses of Iminophosphomamido Chlorogermylenes and Their Complexation with a Rhodium(I) Complex

Electrophilic Behavior of the “Nucleophilic” Pyramidane: Reactivity of Ge‐Pyramidane towards Organolithium Reagents

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