Browse
Submit Data
Databases
API
Help

Dataset Information

15 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Alkali Metal Complexes of a Bis(diphenylphosphino)methane Functionalized Amidinate Ligand: Synthesis and Luminescence.

ABSTRACT: A novel bis(diphenylphosphino)methane (DPPM) functionalized amidine ligand (DPPM-C(N-Dipp)₂ H) (Dipp=2,6-diisopropylphenyl) was synthesized. Subsequent deprotonation with suitable alkali metal bases resulted in the corresponding complexes [M{DPPM-C(N-Dipp)₂ }(L_n )] (M=Li, Na, K, Rb, Cs; L=thf, Et₂ O). The alkali metal complexes form monomeric species in the solid state, exhibiting intramolecular metal-π-interactions. In addition, a caesium derivative [Cs{PPh₂ CH₂ -C(N-Dipp)₂ }]₆ was obtained by cleavage of a diphenylphosphino moiety, forming an unusual six-membered ring structure in the solid state. All complexes were fully characterized by single crystal X-ray diffraction, NMR spectroscopy, IR spectroscopy as well as elemental analysis. Furthermore, the photoluminescent properties of the complexes were thoroughly investigated, revealing differences in emission with regards to the respective alkali metal. Interestingly, the hexanuclear [Cs{PPh₂ CH₂ -C(N-Dipp)₂ }]₆ metallocycle exhibits a blue emission in the solid state, which is significantly red-shifted at low temperatures. The bifunctional design of the ligand, featuring orthogonal donor atoms (N vs. P) and a high steric demand, is highly promising for the construction of advanced metal and main group complexes.

SUBMITTER: Zovko C

PROVIDER: S-EPMC8596514 | biostudies-literature |

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Similar Datasets

Efficient Blue Phosphorescence in Gold(I)-Acetylide Functionalized Coinage Metal Bis(amidinate) Complexes.

Project description:The synthesis of linear symmetric ethynyl- and acetylide-amidinates of the coinage metals is presented. Starting with the desilylation of the complexes [{Me3 SiC?CC(NDipp)2 }2 M2 ] (Dipp=2,6-diisopropylphenyl) (M=Cu, Au) it is demonstrated that this compound class is suitable to serve as a versatile metalloligand. Deprotonation with n-butyllithium and subsequent salt metathesis reactions yield symmetric tetranuclear gold(I) acetylide complexes of the form [{(PPh3 )AuC?CC(NDipp)2 }2 M2 ] (M=Cu, Au). The corresponding Ag complex [{(PPh3 )AuC?CC(NDipp)2 }2 Ag2 ] was obtained by a different route via metal rearrangement. All compounds show bright blue or blue-green microsecond long phosphorescence in the solid state, hence their photophysical properties were thoroughly investigated in a temperature range of 20-295?K. Emission quantum yields of up to 41?% at room temperature were determined. Furthermore, similar emissions with quantum yields of 15?% were observed for the two most brightly luminescent complexes in thf solution.

| S-EPMC7756867 | biostudies-literature

Bis(4-benzhydryl-benzoxazol-2-yl)methane - from a Bulky NacNac Alternative to a Trianion in Alkali Metal Complexes.

Project description:A novel sterically demanding bis(4-benzhydryl-benzoxazol-2-yl)methane ligand 6 (4-BzhH2 BoxCH2 ) was gained in a straightforward six-step synthesis. Starting from this ligand monomeric [M(4-BzhH2 BoxCH)] (M=Na (7), K (81 )) and dimeric [{M(4-BzhH2 BoxCH)}2 ] (M=K (82 ), Rb (9), Cs (10)) alkali metal complexes were synthesised by deprotonation. Abstraction of the potassium ion of 8 by reaction with 18-crown-6 resulted in the solvent separated ion pair [{(THF)2 K@(18-crown-6)}{bis(4-benzhydryl-benzoxazol-2-yl)methanide}] (11), including the energetically favoured monoanionic (E,E)-(4-BzhH2 BoxCH) ligand. Further reaction of 4-BzhH2 BoxCH2 with three equivalents KH and two equivalents 18-crown-6 yielded polymeric [{(THF)2 K@(18-crown-6)}{K@(18-crown-6)K(4-Bzh BoxCH)}]n (n→∞) (12) containing a trianionic ligand. The neutral ligand and herein reported alkali complexes were characterised by single X-ray analyses identifying the latter as a promising precursor for low-valent main group complexes.

| S-EPMC8361911 | biostudies-literature

Alkali metal complexes of an enantiopure iminophosphonamide ligand with bright delayed fluorescence.

Project description:The enantiomerically pure ligand P,P-diphenyl-N,N'-bis((R)-1-phenylethyl)phosphinimidic amide (1; (R)-HPEPIA) was synthesized and subsequently deprotonated with alkali metal precursors to yield dimeric complexes [M2{(R)-PEPIA}2] (M = Li (2), Na (3), K (4), Rb (5)). The cesium compound [M{(R)-PEPIA}] (6) crystallized as a cocrystal composed of dimeric ([Cs2{(R)-PEPIA}2] (6d ) and 1D-polymeric ([Cs{(R)-PEPIA}] n ) (6p ) species in a 1 : 1 ratio. The coordination polymer 6p features a unique sinus-shaped configuration of repeating -Cs-N-P-N-Cs-N-P-N- units. Unusual photoluminescence (PL) properties were found for solid 1-6: in contrast to the fluorescent ligand 1, the alkali metal complexes show phosphorescence at low temperatures (<100 K) and thermally activated delayed fluorescence (TADF) above ∼150 K. The latter provides for PL quantum yields up to 36% (3) at ambient temperature. DFT calculations support that both 1 and 2-6d have similar singlet and triplet excited states with energy separations of a few tens of meV. The strongly enhanced intersystem crossing (ISC) in the metal complexes, resulting in TADF, is attributed to their dimeric structure. This suggests that the fluorophore dimerization may serve as a tool to effect ISC for the design of TADF emitters.

| S-EPMC6510313 | biostudies-literature

Noble Metal Complexes of a Bis-Caffeine Containing NHC Ligand.

Project description:N-Heterocyclic carbenes (NHCs) have seen more and more use over the years. The go-to systems that are usually considered are derivatives of benzimidazole or imidazole. Caffeine possesses an imidazole unit and was already utilized as a carbene-type ligand; however, its use within a tridentate bis-NHC system has-to the best of our knowledge-not been reported so far. The synthesis of the ligand is straightforward and metal complexes are readily available via silver-salt metathesis. A platinum(II) and a palladium(II) complex were isolated and a crystal structure of the former was examined. For the Pt(II) complex, luminescence is observed in solid state as well as in solution.

| S-EPMC9268361 | biostudies-literature

A Phosphine Functionalized β-Diketimine Ligand for the Synthesis of Manifold Metal Complexes.

Project description:A bis(diphenyl)-phosphine functionalized β-diketimine (PNac-H) was synthesized as a flexible ligand for transition metal complexes. The newly designed ligand features symmetrically placed phosphine moieties around a β-diketimine unit, forming a PNNP-type pocket. Due to the hard and soft donor atoms (N vs. P) the ligand can stabilize various coordination polyhedra. A complete series ranging from coordination numbers 2 to 6 was realized. Linear, trigonal planar, square planar, tetrahedral, square pyramidal, and octahedral coordination arrangements containing the PNac-ligand around the metal center were observed by using suitable metal sources. Hereby, PNac-H or its anion PNac- acts as mono-, bi- and tetradendate ligand. Such a broad flexibility is unusual for a rigid tetradentate system. The structural motifs were realized by treatment of PNac-H with a series of late transition metal precursors, for example, silver, gold, nickel, copper, platinum, and rhodium. The new complexes have been fully characterized by single crystal X-ray diffraction, NMR, IR, UV/Vis spectroscopy, mass spectrometry as well as elemental analysis. Additionally, selected complexes were investigated regarding their photophysical properties. Thus, PNac-H proved to be an ideal ligand platform for the selective coordination and stabilization of various metal ions in diverse polyhedra and oxidation states.

| S-EPMC7693294 | biostudies-literature

Assessing Alkali-Metal Effects in the Structures and Reactivity of Mixed-Ligand Alkyl/Alkoxide Alkali-Metal Magnesiates.

Project description:Advancing the understanding of using alkali-metal alkoxides as additives to organomagnesium reagents in Mg-Br exchange reactions, a homologous series of mixed-ligand alkyl/alkoxide alkali-metal magnesiates [MMg(CH2 SiMe3 )2 (dmem)]2 [dmem=2-{[2-(dimethylamino)ethyl]methylamino} ethoxide; M=Li, 1; Na, 2; (THF)K, 3] has been prepared. Structural and spectroscopic studies have established the constitutions of these heteroleptic/heterometallic species, which are retained in arene solution. Evaluation of their reactivity towards 2-bromoanisole has uncovered a marked alkali-metal effect with potassium magnesiate 3 being the most efficient of the three ate reagents. Studies probing the constitution of the exchange product from this reaction suggest that the putative [KMgAr2 (dmem)]2 (Ar=o-OMe-C6 H4 ) intermediate undergoes redistribution into its single metal components [KAr]n and [MgAr(dmem)]2 (5). This process can be circumvented by using a different potassium alkoxide containing an aliphatic chain such as KOR' (R'=2-ethylhexyl) which undergoes co-complexation with Mg(CH2 SiMe3 ) to give [KMg(CH2 SiMe3 )2 (OR')]2 (7). This ate, in turn, reacts quantitatively with 2-bromoanisole furnishing [KMgAr2 (OR')]2 (9) which is stable in solution as a bimetallic compound. Collectively this work highlights the complexity of these alkali-metal mediated Mg-Br exchange reactions, where each reaction component can have a profound effect not only on the success of the reaction; but also the stability of the final metalated intermediates prior to their electrophilic interception.

| S-EPMC9306829 | biostudies-literature

Structural Diversity in Alkali Metal and Alkali Metal Magnesiate Chemistry of the Bulky 2,6-Diisopropyl-N-(trimethylsilyl)anilino Ligand.

Project description:Bulky amido ligands are precious in s-block chemistry, since they can implant complementary strong basic and weak nucleophilic properties within compounds. Recent work has shown the pivotal importance of the base structure with enhancement of basicity and extraordinary regioselectivities possible for cyclic alkali metal magnesiates containing mixed n-butyl/amido ligand sets. This work advances alkali metal and alkali metal magnesiate chemistry of the bulky arylsilyl amido ligand [N(SiMe3 )(Dipp)]- (Dipp=2,6-iPr2 -C6 H3 ). Infinite chain structures of the parent sodium and potassium amides are disclosed, adding to the few known crystallographically characterised unsolvated s-block metal amides. Solvation by N,N,N',N'',N''-pentamethyldiethylenetriamine (PMDETA) or N,N,N',N'-tetramethylethylenediamine (TMEDA) gives molecular variants of the lithium and sodium amides; whereas for potassium, PMDETA gives a molecular structure, TMEDA affords a novel, hemi-solvated infinite chain. Crystal structures of the first magnesiate examples of this amide in [MMg{N(SiMe3 )(Dipp)}2 (?-nBu)]? (M=Na or K) are also revealed, though these breakdown to their homometallic components in donor solvents as revealed through NMR and DOSY studies.

| S-EPMC5096043 | biostudies-literature

Open-Ended Metallodithiolene Complexes with the 1,2,4,5-Tetrakis(diphenylphosphino)benzene Ligand: Modular Building Elements for the Synthesis of Multimetal Complexes.

Project description:Open-ended, singly metalated dithiolene complexes with 1,2,4,5-tetrakis(diphenylphosphino)benzene (tpbz) are prepared either by ligand transfer to [Cl2M(tpbz)] from (R2C2S2)SnR'2 (R = CN, R' = Me; R = Me, R' = nBu) or by a direct reaction between tpbz and [M(S2C2R2)2] (M = Ni, Pd, Pt; R = Ph, p-anisyl) in a 1:1 ratio. The formation of dimetallic [(R2C2S2)M(tpbz)M(S2C2R2)] attends these syntheses in modest amounts, but the open-ended compounds are readily separated by silica chromatography. As affirmed by X-ray crystallographic characterization of numerous members of the set, the [(R2C2S2)M(tpbz)] compounds show dithiolene ligands in their fully reduced ene-1,2-dithiolate form conjoined with divalent Group 10 ions. Minor amounts of octahedral [(Ph2C2S2)2PtIV(tpbz)], a presumed intermediate, are isolated from the preparation of [(Ph2C2S2)PtII(tpbz)]. Heterodimetallic [(Ph2C2S2)Pt(tpbz)Ni(S2C2Me2)] is prepared from [(Ph2C2S2)PtII(tpbz)]; its cyclic voltammogram, upon anodic scanning, shows two pairs of closely spaced, but resolved, 1e- oxidations corresponding first to [R2C2S22-] - 1e- → [R2C2S•S-] and then to [R2C2S•S-] - 1e- → [R2(C═S)2]. The open diphosphine of [(R2C2S2)M(tpbz)] can be oxidized to afford open-ended [(R2C2S2)M(tpbzE2)] (E = O, S). Synthesis of the octahedral [(dppbO2)3Ni][I3]2 [dppbO2 = 1,2-bis(diphenylphosphoryl)benzene] suggests that the steric profile of [(R2C2S2)M(tpbzE2)] is moderated enough that three could be accommodated as ligands around a metal ion.

| S-EPMC8424627 | biostudies-literature

Metal Complexes of the Porphyrin-Functionalized Polybenzoxazine.

Project description:New porphyrin-functionalized benzoxazine (Por-BZ) in high purity and yield was synthesized in this study based on 1H and 13C NMR and FTIR spectroscopic analyses through the reduction of Schiff base formed from tetrakis(4-aminophenyl)porphyrin (TAPP) and salicylaldehyde and the subsequent reaction with CH2O. Thermal properties of the product formed through ring-opening polymerization (ROP) of Por-BZ were measured using DSC, TGA and FTIR spectroscopy. Because of the rigid structure of the porphyrin moiety appended to the benzoxazine unit, the temperature required for ROP (314 °C) was higher than the typical Pa-type benzoxazine monomer (ca. 260 °C); furthermore, poly(Por-BZ) possessed a high thermal decomposition temperature (Td10 = 478 °C) and char yield (66 wt%) after thermal polymerization at 240 °C. An investigation of the thermal and luminescence properties of metal-porphyrin complexes revealed that the insertion of Ni and Zn ions decreased the thermal ROP temperatures of the Por-BZ/Ni and Por-BZ/Zn complexes significantly, to 241 and 231 °C, respectively. The metal ions acted as the effective promoter and catalyst for the thermal polymerization of the Por-BZ monomer, and also improved the thermal stabilities after thermal polymerization.

| S-EPMC8839356 | biostudies-literature

Alkali metal control over N-N cleavage in iron complexes.

Project description:Though N2 cleavage on K-promoted Fe surfaces is important in the large-scale Haber-Bosch process, there is still ambiguity about the number of Fe atoms involved during the N-N cleaving step and the interactions responsible for the promoting ability of K. This work explores a molecular Fe system for N2 reduction, particularly focusing on the differences in the results obtained using different alkali metals as reductants (Na, K, Rb, Cs). The products of these reactions feature new types of Fe-N2 and Fe-nitride cores. Surprisingly, adding more equivalents of reductant to the system gives a product in which the N-N bond is not cleaved, indicating that the reducing power is not the most important factor that determines the extent of N2 activation. On the other hand, the results suggest that the size of the alkali metal cation can control the number of Fe atoms that can approach N2, which in turn controls the ability to achieve N2 cleavage. The accumulated results indicate that cleaving the triple N-N bond to nitrides is facilitated by simultaneous approach of least three low-valent Fe atoms to a single molecule of N2.

| S-EPMC4277784 | biostudies-literature

OmicsDI is part of the ELIXIR infrastructure

OmicsDI is an Elixir interoperability service. Learn more ›

Tweets

OmicsDI Databases

PRIDE
PeptideAtlas
MassIVE
JPOST Repository
Physiome Model Repository

EGA
EVA
ENA
LINCS
PAXDB
Cell Collective

MetaboLights
Metabolomics Workbench
MetabolomeExpress
GNPS
BioModels
FAIRDOMHub

ArrayExpress
dbGaP
ExpressionAtlas
GEO
NODE

Information

Databases
Help
API
Contact us
Code on GitHub
Terms of use
Submit Data