Selective one-pot syntheses of PtII–CuI heterobimetallic complexes of 4,5-diazafluorenide derivatives

Batcup, Rhys; Chiu, Frederick Sin Nang; Annibale, Vincent T.; Huh, Jung-Eun Ustina; Tan, Runyu; Song, Datong

doi:10.1039/c3dt52135d

Cited by 9 publications

(27 citation statements)

References 30 publications

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“…Along these lines, Song and co-workers have explored the coordination chemistry of daf and substituted diazafluorenes, including significant work aimed at leveraging this unique acid/base chemistry [15]. In their work, Song and co-workers have found that the acidic C-H bonds of daf can undergo deprotonation that results in follow-up reactivity [16][17][18][19][20]. More broadly, Stahl [21][22][23] and several other groups [24][25][26] have developed a number of catalyst systems supported by diazafluorene ligands.…”

Section: Introductionmentioning

confidence: 99%

4,5-Diazafluorene and 9,9’-Dimethyl-4,5-Diazafluorene as Ligands Supporting Redox-Active Mn and Ru Complexes

et al. 2020

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4,5-diazafluorene (daf) and 9,9’-dimethyl-4,5-diazafluorene (Me2daf) are structurally similar to the important ligand 2,2’-bipyridine (bpy), but significantly less is known about the redox and spectroscopic properties of metal complexes containing Me2daf as a ligand than those containing bpy. New complexes Mn(CO)3Br(daf) (2), Mn(CO)3Br(Me2daf) (3), and [Ru(Me2daf)3](PF6)2 (5) have been prepared and fully characterized to understand the influence of the Me2daf framework on their chemical and electrochemical properties. Structural data for 2, 3, and 5 from single-crystal X-ray diffraction analysis reveal a distinctive widening of the daf and Me2daf chelate angles in comparison to the analogous Mn(CO)3(bpy)Br (1) and [Ru(bpy)3]2+ (4) complexes. Electronic absorption data for these complexes confirm the electronic similarity of daf, Me2daf, and bpy, as spectra are dominated in each case by metal-to-ligand charge transfer bands in the visible region. However, the electrochemical properties of 2, 3, and 5 reveal that the redox-active Me2daf framework in 3 and 5 undergoes reduction at a slightly more negative potential than that of bpy in 1 and 4. Taken together, the results indicate that Me2daf could be useful for preparation of a variety of new redox-active compounds, as it retains the useful redox-active nature of bpy but lacks the acidic, benzylic C–H bonds that can induce secondary reactivity in complexes bearing daf.

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Section: Introductionmentioning

confidence: 99%

4,5-Diazafluorene and 9,9’-Dimethyl-4,5-Diazafluorene as Ligands Supporting Redox-Active Mn and Ru Complexes

et al. 2020

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“…The reaction of (NHC)M C X with compounds of other metals in the anionic species, negative charge of which is localized at the organic ligand, can be useful for the realization of path 2b [191]. The coordination at the coordination active site with the formation of bimetallic cationic species instead of transmetalation has been also observed using the chelate iridium cyclometalated [184] and ferrocene [192] structures in the presence of KPF 4 as source of the non-nucleophilic coordination anion.…”

Section: Reactions With the Formation Of Bimetallic Adducts Retaining The Nhc-m с Bondmentioning

confidence: 94%

Alternative Transformations of N-Heterocyclic Carbene Complexes of the Group 11 Metals in Transmetalation Reactions (A Review)

Mikhaylov

Балова

2021

Russ J Gen Chem

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The carbene transfer from N-heterocyclic carbene complexes of Group 11 metals (NHC-M C ) (especially silver and copper) to other metals is considered a convenient and universal, sometimes having no alternative, method for the synthesis of a wide range of important N-heterocyclic carbene complexes of transition metals. As the number of successful examples of transmetalation with the formation of the target product has increased, the data were accumulated on alternative or unexpected results of the interaction of NHC-M C complexes with compounds of other metals. This review considers the examples of NHC-M C reactions with compounds of other metals which proceed with a change in the metals oxidation state, conversion of (NHC)M C X into cationic homoleptic [(NHC) 2 M C ] + forms, transmetalation retaining the other metal in the coordination sphere of the product, or formation of heterometallic adducts preserving the M C -C carbene bond, rather than these occurring according to the standard reaction pathway. Unusual "reverse" carbene transfer reactions have been considered separately. The review material reveals a promising new synthetic potential of NHC-M C in the reactions with other metals and discusses the possible mechanisms and driving forces of such transformations. The most important aspects of the application of the obtained products, primarily in various catalytic processes, have been considered as well.

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“…26 Surprisingly when the metallation sequence is reversed and the [Cu(daf )(IPr)] complex is treated with [Pt(Ph) 2 (μ-SMe 2 ] n (n = 2 or 3), the exact same Pt(II)-Cu(I) heterobimetallic complex (as opposed to an isomer) was obtained. 26 In the process of generating [(IPr)Cu(daf )Pt(Ph) 2 ] from [Cu(daf )(IPr)] the {Cu(IPr)} + fragment was replaced by the {Pt(Ph) 2 } unit at the N,N-chelate site and migrated to the backbone C-donor. The built-in self-correction featured in the synthesis of the [(IPr)Cu(daf )Pt(Ph) 2 ] system allowed for a one pot synthesis to be successfully carried out (Scheme 4).…”

Section: Ii1 Coordination Chemistry Of the Parent Dafh And Daf − LImentioning

confidence: 99%

“…The synthesis of these Pt II -Cu I heterobimetallics is highly regioselective, and can also be performed in one-pot (Scheme 6). 26…”

mentioning

confidence: 99%

Coordination chemistry and applications of versatile 4,5-diazafluorene derivatives

Annibale

Song

2016

Dalton Trans.

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This perspective review will examine the coordination chemistry and applications of metal complexes of 4,5-diazafluorene derivatives. The versatile derivatives of 4,5-diazafluorene can serve multiple roles, and display a number of coordination modes. The ambidentate derivatives with multiple coordination sites can allow for the syntheses of coordination polymers, multimetallic, and macrocyclic complexes. In addition, certain 4,5-diazafluorene derivatives can serve as spectator ligands to support reactivity at the metal centre, or as reactive actor ligands engaging in atypical reactivity patterns. The applications of metal complexes of 4,5-diazafluorene derivatives in catalysis, photochemistry and photophysics, as well as in bioinorganic chemistry are also surveyed.

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Selective one-pot syntheses of PtII–CuI heterobimetallic complexes of 4,5-diazafluorenide derivatives

Cited by 9 publications

References 30 publications

4,5-Diazafluorene and 9,9’-Dimethyl-4,5-Diazafluorene as Ligands Supporting Redox-Active Mn and Ru Complexes

4,5-Diazafluorene and 9,9’-Dimethyl-4,5-Diazafluorene as Ligands Supporting Redox-Active Mn and Ru Complexes

Alternative Transformations of N-Heterocyclic Carbene Complexes of the Group 11 Metals in Transmetalation Reactions (A Review)

Coordination chemistry and applications of versatile 4,5-diazafluorene derivatives

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