A Sterically Encumbered 13/15 Cycle and its Cleavage with <i>N</i>‐heterocyclic Carbenes and other Lewis Bases

Kapitein, Manuel; Balmer, Michael; Hänisch, Carsten von

doi:10.1002/zaac.201600263

Cited by 11 publications

(4 citation statements)

References 44 publications

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“…A series of NHC-stabilized monomeric group 13 metalsilylphosphanides [(NHC)R 2 M−P(H)Si t BuPh 2 ] 422, 423 (Figure 46) were achieved through the cleavage of the fourmembered cyclic compounds [R 2 M−P(H)Si t BuPh 2 ] 2 (M = Al, Ga, In) upon treatment with NHCs. 423,424 The solid-state structure of 422 revealed a cis-orientation of the NHC and the silyl group relative to the M−P bond axis, while a trans-orientation was found for complexes 423a−d. 46).…”

Section: Nhc Adducts Of Aluminum In Low Oxidationmentioning

confidence: 99%

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NHCs in Main Group Chemistry

et al. 2018

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Since the discovery of the first stable N-heterocyclic carbene (NHC) in the beginning of the 1990s, these divalent carbon species have become a common and available class of compounds, which have found numerous applications in academic and industrial research. Their important role as two-electron donor ligands, especially in transition metal chemistry and catalysis, is difficult to overestimate. In the past decade, there has been tremendous research attention given to the chemistry of low-coordinate main group element compounds. Significant progress has been achieved in stabilization and isolation of such species as Lewis acid/base adducts with highly tunable NHC ligands. This has allowed investigation of numerous novel types of compounds with unique electronic structures and opened new opportunities in the rational design of novel organic catalysts and materials. This Review gives a general overview of this research, basic synthetic approaches, key features of NHC-main group element adducts, and might be useful for the broad research community.

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Section: Nhc Adducts Of Aluminum In Low Oxidationmentioning

confidence: 99%

“…A series of NHC-stabilized monomeric group 13 metalsilylphosphanides [(NHC)R 2 M–P(H)Si t BuPh 2 ] 422 , 423 (Figure ) were achieved through the cleavage of the four-membered cyclic compounds [R 2 M–P(H)Si t BuPh 2 ] 2 (M = Al, Ga, In) upon treatment with NHCs. , …”

Section: Nhc Complexes Of Main Group Elementsmentioning

confidence: 99%

NHCs in Main Group Chemistry

et al. 2018

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“…The bond lengths of Ga–Cl and Ga–N are 2.2293(10) and 2.013(3) Å, respectively. These lengths are comparable to those observed in the usual terminal Ga–Cl single bonds (2.22–2.29 Å) and the nitrogen to gallium coordination bonds (2.01–2.08 Å). , The CC and C–C bond lengths within the GaC 4 ring are 1.343(5)–1.349(4) and 1.529(5) Å, respectively, which are within the ranges in those reported for Lewis-base coordinated gallole derivatives (1.34–1.36 and 1.51–1.53 Å, respectively). , …”

Section: Resultsmentioning

confidence: 99%

Ten-Membered Cyclodecatetraene Derivatives Including Two Gallium Atoms: Experimental and Theoretical Studies on Synthesis, Structures, and Their Transformations to Nine- and Five-Membered Gallacycles

et al. 2023

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The chemistry of medium-sized ring compounds, including group 13 elements, has scarcely been investigated. Herein, we report that 5,10-digallacyclodeca-1,3,6,8-tetraene derivatives Cl 2 Ga 2 C 8 R 8 (R = Me (5a), Et (5b)) can be obtained by the reaction of GaCl 3 and zirconacyclopentadiene Cp 2 ZrC 4 R 4 (R = Me (2a), Et (2b), Cp: η 5 -C 5 H 5 ) in toluene. X-ray crystal structure analysis revealed that compound 5b has a 10-membered cyclodecatetraene structure composed of two butadiene skeletons and two GaCl fragments. X-ray crystal structure analysis and IR measurement confirmed that compound 5b forms Ga 2 Cl 2 four-membered rings via intermolecular Cl to Ga donor−acceptor interactions, which result in the formation of oligomeric chain structures in the solid state and toluene solution. The treatment of compound 5b with 2 equivalents of 4-(dimethylamino)pyridine (DMAP) proceeded via the coordination of DMAP to the Ga center and the ring contraction to give DMAP-coordinated five-membered gallole Cl(DMAP)GaC 4 Et 4 (4bDMAP). The reaction of compound 5a with 2 equivalents of MesLi (Mes: 2,4,6-Me 3 C 6 H 2 ) in toluene to form a 9,10-digallabicyclo[4.3.1]decatriene derivative (MesGaC 8 Me 8 )GaMes (6a) caused ring contraction. Theoretical investigation revealed that the 10-membered ring derivative, Cl 2 Ga 2 C 8 H 8 (GaH-10), is formed by the dimerization of two gallole molecules, ClGaC 4 H 4 (GaH-5), via the addition of two Ga−C bonds without an energy barrier. The immediate formation of GaH-10 was attributed to the transannular electronic interaction between the expanded empty p-orbital on the Ga atom and the electron-rich sp 2 carbons of the C�C double bond in GaH-5. Moreover, GaH-10 and one of the isomer, nine-membered ring derivative (ClGaC 8 H 8 )GaCl, were found to be thermodynamically more stable, as compared to GaH-5.

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“…However, when the substituents on Ga are bulkier, they observed that using a strong σ‐donor Lewis base is not enough to cleave the oligomeric heterocycle when the steric demand is high. Thus, pyridine, DMAP and IPr (1,3‐di iso propyl‐4,5‐dimethylimidazole‐2‐ylidene) can coordinate ( IV ) [10c] . Only IMes and IDip can provide such stabilization after a rearrangement if the group at the phosphorous terminal is large ( V ) [10a] …”

Section: Introductionmentioning

confidence: 99%

Synthesis, Structure, and Bonding Analysis of Lewis Base and Lewis Acid/Base‐Stabilized Phosphanylgallanes

2022

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Phosphanylgallane with hydrogen and halogen substituents (RXGa−PHR, R=organic substituent, X=halogen/hydrogen) are regarded as putative suitable precursors for accessing Ga=P doubly bonded species. Herein, we report on the synthesis, structure, and bonding analysis of a series of Lewis base‐ and Lewis acid/base‐stabilized phosphanylgallane bearing P−H and Ga−Cl/H substitution. To avoid oligomerization, the treatment of IDip.GaCl3 and (IDip)GaH2Cl (IDip=1,3‐bis(2,6‐diisopropylphenyl) imidazole‐2‐ylidene) with LiPHR or LiPHR(BH3) (R=Ph, Tip, Mes, NiPr2, NCy2) affords the corresponding Lewis base and Lewis acid/base coordinated H,Cl‐functionalized monomeric phosphanylgallane, respectively. The structure of these derivatives were determined by spectroscopic and X‐ray crystallographic analyses. The observed Ga−P bond lengths are comparable to those previously reported phosphanylgallane analogues. The nature of the CIDip‐Ga coordination bond was assessed with Energy Decomposition Analysis, suggesting a relatively stable adduct. Reactions of the phosphanylgallane with Brønsted bases were investigated.

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A Sterically Encumbered 13/15 Cycle and its Cleavage with N‐heterocyclic Carbenes and other Lewis Bases

Cited by 11 publications

References 44 publications

NHCs in Main Group Chemistry

NHCs in Main Group Chemistry

Ten-Membered Cyclodecatetraene Derivatives Including Two Gallium Atoms: Experimental and Theoretical Studies on Synthesis, Structures, and Their Transformations to Nine- and Five-Membered Gallacycles

Synthesis, Structure, and Bonding Analysis of Lewis Base and Lewis Acid/Base‐Stabilized Phosphanylgallanes

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