Synthesis and Properties of Hydrazino Amino Acyclic Carbenes of Gold(I), Platinum(II), Palladium(II) and Rhodium(III)

Tšupova, Svetlana; Rudolph, Matthias; Röminger, Frank; Hashmi, A. Stephen K.

doi:10.1002/adsc.201600615

Cited by 28 publications

(19 citation statements)

References 57 publications

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“…Previous studies on this cycloisomerization reaction have shown 95 % yield in 12 hours using 5 mol % of AuCl 3 or 79 % after 36 hours, employing a lower catalyst loading of a phosphine‐based complex (1.0 mol % (Ph 3 P)AuNTf 2 ) . Recently, some examples of HAAC (Hydrazino amino acyclic carbene) complexes were developed in our group, that gave up to 100 % yield, but at the expense of a prolonged reaction time (2 days) …”

Section: Resultsmentioning

confidence: 99%

Gold(I) Complexes Stabilized by Nine‐ and Ten‐Membered N‐Heterocyclic Carbene Ligands

Cervantes‐Reyes

Röminger

Rudolph

et al. 2019

Chemistry A European J

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Nine-and ten-membered N-heterocyclic carbene (NHC) ligands have been developed and for the first time their gold(I)c omplexes weres ynthesized. The protonated NHC pro-ligands 2a-h were preparedb yt he reactiono f readily available N,N'-diarylformamidines with bis-electrophilic buildingb locks, followed by anion exchange. In situ deprotonation of the tetrafluoroborates 2a-h with tBuOK in the presence of AuCl(SMe 2 )p rovided fast access to NHCgold(I) complexes 3-10.T hese new NHC-gold(I) complexes show very good catalytic activity in ac ycloisomerization reaction( 0.1 mol %c atalystl oading, up to 100 %c onversion) and their solid-state structures revealh igh steric hindrance aroundt he metal atom (%V bur up to 53.0) which is caused by their expanded-ringarchitecture. Results and DiscussionExpanded-ring NHC pro-ligands Various reactionc onditions have been previously reported for the synthesis of six-and seven-memberedp rotonated NHC salts, including the classic ring-closure of ad isubstituted alkyl or aryl amino moiety with ap re-carbenic unit (e.g. HC(OEt) 3 or formaldehyde). [15] Despite the good yields, those conditions are limitedw ith regard to the bulkiness of the N-substituted backbone.L argere ight-membered ring NHCs alts have been syn- [a] A.

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Section: Resultsmentioning

confidence: 99%

Gold(I) Complexes Stabilized by Nine‐ and Ten‐Membered N‐Heterocyclic Carbene Ligands

Cervantes‐Reyes

Röminger

Rudolph

et al. 2019

Chemistry A European J

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“…This reaction has previously been used to benchmark catalyst activity and the effectiveness of added activators in homogenous gold catalysis. [31][32][33][34] The reaction was performed with 2 mol % of chloro(triphenylphosphine) gold and an equimolar amount of the halide abstracting agent in deuterated chloroform as solvent.…”

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confidence: 99%

Activation of a Metal‐Halogen Bond by Halogen Bonding

et al. 2020

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In recent years, the non‐covalent interaction of halogen bonding (XB) has found increasing application in organocatalysis. However, reports of the activation of metal‐ligand bonds by XB have so far been limited to a few reactions with elemental iodine or bromine. Herein, we present the activation of metal‐halogen bonds by two classes of inert halogen bond donors and the use of the resulting activated complexes in homogenous gold catalysis. The only recently explored class of iodolium derivatives were shown to be effective activators in two test reactions and their activity could be modulated by blocking of the Lewis acidic sites. Bis(benzimidazolium)‐based halogen bonding activators provided even more rapid conversion, while the non‐iodinated reference compound showed little activity. The role of halogen bonding in the activation of metal‐halogen bonds was further investigated by NMR experiments and DFT calculations, which support the mode of activation occurring via halogen bonding.

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“…The presence of only one C≡N peak indicates on the presence in the structure of one unreacted isocyanide ligand. The longwave shift of the C≡N peak on the transition PdCl 2 (CNR) 2 → PdCl 2 (ADC)(CNR) accords with higher σ-donating ability of the ADC ligand compared to isocyanide [53][54][55][56][57].…”

Section: Resultsmentioning

confidence: 81%

Polystyrene-Supported Acyclic Diaminocarbene Palladium Complexes in Sonogashira Cross-Coupling: Stability vs. Catalytic Activity

et al. 2018

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Two types of immobilized on the amino-functionalized polystyrene-supported acyclic diaminocarbene palladium complexes (ADC-Pd II ) are investigated under Sonogashira cross-coupling conditions. Depending on substituents in the diaminocarbene fragment immobilized ADC-Pd II , systems are found to have different catalytic activity and stability regarding Pd-leaching. Pd II -diaminocarbenes possessing protons at both nitrogen atoms smoothly decompose into Pd 0 -containing species providing a catalytic "cocktail system" with high activity and ability to reuse within nine runs. Polymer-supported palladium (II) complex bearing NBn-C carbene -NH-moiety exhibits greater stability while noticeably lower activity under Sonogashira cross-coupling. Four molecular ADC-Pd II complexes are also synthesized and investigated with the aim of confirming proposed base-promoted pathway of ADC-Pd II conversion through carbodiimide into an active Pd 0 forms.

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Synthesis and Properties of Hydrazino Amino Acyclic Carbenes of Gold(I), Platinum(II), Palladium(II) and Rhodium(III)

Cited by 28 publications

References 57 publications

Gold(I) Complexes Stabilized by Nine‐ and Ten‐Membered N‐Heterocyclic Carbene Ligands

Gold(I) Complexes Stabilized by Nine‐ and Ten‐Membered N‐Heterocyclic Carbene Ligands

Activation of a Metal‐Halogen Bond by Halogen Bonding

Polystyrene-Supported Acyclic Diaminocarbene Palladium Complexes in Sonogashira Cross-Coupling: Stability vs. Catalytic Activity

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