Browse
Submit Data
Databases
API
Help

Dataset Information

0 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Metallation of sensitive fluoroarenes using a potassium TMP-zincate supported by a silyl(bis)amido ligand.

ABSTRACT: Combining a bulky bis(amide) and a reactive one-coordinate TMP (2,2,6,6-tetramethylpiperidide) ligand, a new mixed K/Zn heteroleptic base has been developed for regioselective zincation of fluoroarenes. This special ligand set allows for trapping and structural authentication of the first intermediates of direct Zn-H exchange of fluoroarenes obtained via deprotonative metallation, providing mechanistic insights of the processes involved.

SUBMITTER: Mastropierro P

PROVIDER: S-EPMC9040423 | biostudies-literature | 2022 Apr

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Publications

Metallation of sensitive fluoroarenes using a potassium TMP-zincate supported by a silyl(bis)amido ligand.

Mastropierro Pasquale P Kennedy Alan R AR Hevia Eva E

Chemical communications (Cambridge, England) 20220426 34

Combining a bulky bis(amide) and a reactive one-coordinate TMP (2,2,6,6-tetramethylpiperidide) ligand, a new mixed K/Zn heteroleptic base has been developed for regioselective zincation of fluoroarenes. This special ligand set allows for trapping and structural authentication of the first intermediates of direct Zn-H exchange of fluoroarenes obtained <i>via</i> deprotonative metallation, providing mechanistic insights of the processes involved. ...[more]

PMID: 35403647

Similar Datasets

[μ-Bis(trimethyl-silyl)amido]bis-[μ-N,N-dimethyl-N',N''-bis-(trimethyl-silyl)guanidinato]-triangulo-tricopper(I).

Project description:The title compound, [Cu(3)(C(6)H(18)NSi(2))(C(9)H(24)N(3)Si(2))(2)], is a trinuclear Cu(I) complex. A crystallographic twofold axis passes through one Cu(I) atom and the N atom of the bis-(trimethyl-silyl)amide ligand that bridges between the other two Cu(I) atoms. The Cu-Cu bonds bridged by the guanadinate ligands [2.7913 (9) Å] are slightly longer than the Cu-Cu bond bridged by the bis-(trimethyl-silyl)amide ligand [2.6405 (11) Å].

| S-EPMC2968876 | biostudies-literature

Bis[μ-N-(tert-butyl-dimethyl-silyl)-N-(pyridin-2-ylmeth-yl)amido]-bis-[methyl-cobalt(II)].

Project description:The green title complex, [Co(2)(CH(3))(2)(C(12)H(21)N(2)Si)(2)], was obtained from bis-{[μ-N-tert-butyl-dimethyl-silyl-N-(pyridin-2-ylmeth-yl)amido]-chloridocobalt(II)} and methyl-lithium in diethyl ether at 195 K via a metathesis reaction. The dimeric cobalt(II) complex exhibits a crystallographic center of inversion in the middle of the Co(2)N(2) ring (average Co-N = 2.050 Å). The Co(II) atom shows a distorted tetra-hedral coordination sphere. The exocyclic Co-N bond length to the pyridyl group shows a similar value of 2.045 (4) Å. The exocyclic methyl group has a rather long Co-C bond length of 2.019 (5) Å.

| S-EPMC3435591 | biostudies-literature

Formation of a hydride containing amido-zincate using pinacolborane.

Project description:Amido-zincates containing hydrides are underexplored yet potentially useful complexes. Attempts to access this type of zincate through combining amido-organo zincates and pinacolborane (HBPin) via Zn-C/H-BPin exchange led instead to preferential formation of amide-BPin and/or [amide-BPin(Y)]- (Y = Ph, amide, H), when the amide is hexamethyldisilazide or 2,2,6,6-tetramethylpiperidide and the hydrocarbyl group was phenyl or ethyl. In contrast, the use of a dipyridylamide (dpa) based arylzinc complex led to Zn-C/H-BPin metathesis being the major outcome. Independent synthesis and full characterisation of two LnLi[(dpa)ZnPh2] (L = THF, n = 3; L = PMDETA, n = 1) complexes, 1 and 3, respectively, enabled reactivity studies that demonstrated that these species display zincate type reactivity (by comparison to the lower reactivity of the neutral complex (Me-dpa)ZnPh2, 4, Me-dpa = 2,2'-dipyridyl-N-methylamine). This included 1 performing the rapid deprotonation of 4-ethynyltoluene and also phenyl transfer to α,α,α-trifluoroacetophenone in contrast to neutral complex 4. Complex 1 reacted with one equivalent of HBPin to give predominantly PhBPin (ca. 90%) and a lithium amidophenylzincate containing a hydride unit, complex 7-A, as the major zinc containing product. Complex 7-A transfers hydride to an electrophile preferentially over phenyl, indicating it reacts as a hydridozincate. Attempts to react 1 with >1 equivalent of HBPin or with catecholborane led to more complex outcomes, which included significant borane and dpaZn substituent scrambling, two examples of which were crystallographically characterised. While this work provides proof of principle for Zn-C/H-BPin exchange as a route to form an amido-zincate containing a hydride, amido-organozincates that undergo more selective Zn-C/H-BPin exchange still are required.

| S-EPMC8507400 | biostudies-literature

Bis[(2-pyridylmeth-yl)(triisopropyl-silyl)amido]zinc(II)-toluene-tetra-hydro-furan (4/2/1).

Project description:The transamination reaction of (2-pyridylmeth-yl)(triiso-propyl-silyl)amine with bis-{bis-(trimethyl-silyl)amido}zinc(II) yields the colorless title solvate, [Zn(C(15)H(27)N(2)Si)(2)]·0.5C(7)H(8)·0.25C(4)H(8)O. The title compound was crystallized from toluene and tetra-hydro-furan. There are two independent mol-ecules in the asymmetric unit. In each mol-ecule, the Zn atom is tetra-hedrally coordinated by four N atoms. The two mol-ecules differ in the orientation of the isopropyl groups. The mol-ecules show large N-Zn-N angles [143.0 (2) and 145.7 (2)° between the amide groups].

| S-EPMC2961323 | biostudies-literature

Structurally defined potassium-mediated zincation of pyridine and 4-R-substituted pyridines (R = Et, iPr, tBu, Ph, and Me2N) by using dialkyl-TMP-zincate bases.

Project description:Two potassium-dialkyl-TMP-zincate bases [(pmdeta)K(mu-Et)(mu-tmp)Zn(Et)] (1) (PMDETA = N,N,N',N'',N''-pentamethyldiethylenetriamine, TMP = 2,2,6,6-tetramethylpiperidide), and [(pmdeta)K(mu-nBu)(mu-tmp)Zn(nBu)] (2), have been synthesized by a simple co-complexation procedure. Treatment of 1 with a series of substituted 4-R-pyridines (R = Me(2)N, H, Et, iPr, tBu, and Ph) gave 2-zincated products of the general formula [{2-Zn(Et)(2)-mu-4-R-C(5)H(3)N}(2)2{K(pmdeta)}] (3-8, respectively) in isolated crystalline yields of 53, 16, 7, 23, 67, and 51%, respectively; the treatment of 2 with 4-tBu-pyridine gave [{2-Zn(nBu)(2)-mu-4-tBu-C(5)H(3)N}(2)2{K(pmdeta)}] (9) in an isolated crystalline yield of 58%. Single-crystal X-ray crystallographic and NMR spectroscopic characterization of 3-9 revealed a novel structural motif consisting of a dianionic dihydroanthracene-like tricyclic ring system with a central diazadicarbadizinca (ZnCN)(2) ring, face-capped on either side by PMDETA-wrapped K(+) cations. All the new metalated pyridine complexes share this dimeric arrangement. As determined by NMR spectroscopic investigations of the reaction filtrates, those solutions producing 3, 7, 8, and 9 appear to be essentially clean reactions, in contrast to those producing 4, 5, and 6, which also contain laterally zincated coproducts. In all of these metalation reactions, the potassium-zincate base acts as an amido transfer agent with a subsequent ligand-exchange mechanism (amido replacing alkyl) inhibited by the coordinative saturation, and thus, low Lewis acidity of the 4-coordinate Zn centers in these dimeric molecules. Studies on analogous trialkyl-zincate reagents in the absence and presence of stoichiometric or substoichiometric amounts of TMP(H) established the importance of Zn-N bonds for efficient zincation.

| S-EPMC3784044 | biostudies-literature

Bis(diethyl-amido-κN)(diethyl-amine-κN)bis-(2,6-diisopropyl-phenyl-amido-κN)zirconium(IV).

Project description:In the title compound, [Zr(C(12)H(18)N)(2)(C(4)H(10)N)(2)(C(4)H(11)N)] or [Zr(HNC(6)H(3) (i)Pr(2))(2)(NEt(2))(2)(HNEt(2))], which was obtained by the reaction of Zr(NEt)(4) with (i)Pr(2)C(6)H(3)NH(2), the Zr(IV) atom is in a trigonal-bipiramidal geometry in which the N atoms from two (i)Pr(2)C(6)H(3)NH and one NEt(2) ligand occupy the equatorial positions, and the N atoms of an NEt(2) and an Et(2)NH ligand occupy the apical positions. An intra-molecular N-H⋯N contact occurs. There are two independent molecules in the asymmetric unit.

| S-EPMC3569177 | biostudies-literature

Bis(2,3-dimethyl-anilinium) tetra-chlorido-zincate dihydrate.

Project description:In the title compound, (C(8)H(12)N)(2)[ZnCl(4)]·2H(2)O, the Zn atom is coordinated by four Cl atoms in a tetra-hedral geometry. The water mol-ecules and the organic cations inter-act with the [ZnCl(4)](2-) complex anions, building up a two-dimensional hydrogen-bonded network parallel to (100).

| S-EPMC3120428 | biostudies-literature

Bis(isoquinolin-2-ium) tetra-chlorido-zincate dihydrate.

Project description:In the title compound, (C9H8N)2[ZnCl4]·2H2O, the tetra-chlorido-zincate ion is located on a twofold rotation axis with the Zn atom on a special position. The crystal packing is stabilized by N-H⋯O and O-H⋯Cl inter-actions.

| S-EPMC4158490 | biostudies-literature

Bis(2,5-dimethyl-anilinium) tetra-chlorido-zincate(II).

Project description:In the title compound, (C(8)H(12)N)(2)[ZnCl(4)], the Zn(2+) ion adopts a distorted tetra-hedral coordination geometry. In the crystal, the cations and anions are linked by N-H⋯Cl hydrogen bonds, leading to ribbons propagating parallel to the a axis.

| S-EPMC2968953 | biostudies-literature

Bis(2,6-dimethyl-pyridinium) tetra-bromido-zincate(II).

Project description:In the crystal structure of the title compound, (C(7)H(10)N)(2)[ZnBr(4)], the coordination geometry of the anion is approximately tetra-hedral and a twofold rotation axis passes through the Zn atom. The Zn-Br bond lengths range from 2.400 (2) to 2.408 (3) Å and the Br-Zn-Br angles range from 108.14 (6) to 115.15 (15)°. In the crystal structure, the [ZnBr(4)](2-) anion is connected to two cations through N-H⋯Br and H(2)C-H⋯Br hydrogen bonds, forming two-dimensional cation-anion-cation layers normal to the b axis. No significant Br⋯Br inter-actions [the shortest being 4.423 (4) Å] are observed in the structure.

| S-EPMC2977623 | 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