7 research outputs found
Platinum-Catalyzed Double Acylation of 2‑(Aryloxy)pyridines via Direct C–H Activation
A unique, platinum-catalyzed,
direct C–H acylation of 2-(aryloxy)Âpyridines
with acyl chlorides is discovered. The reaction requires neither an
oxidant nor other additives. When both <i>ortho</i> positions
of the aryl group are accessible, the double acylation occurs readily
to produce the diacylated products. Aliphatic, aromatic, and α,β-unsaturated
acyl groups can all be introduced. The acylation reaction may proceed
through an analogous aromatic electrophilic substitution triggered
by the nucleophilic attack of the platinum at the acyl chloride
Regiospecific Acylation of Cycloplatinated Complexes: Scope, Limitations, and Mechanistic Implications
A series of platinum
complexes based on the tridentate cyclometalating
ligand derivatives 6-arylamino-2,2′-bipyridine, 6-phenoxy-2,2′-bipyridine,
6-phenylthio-2,2′-bipyridine, 6-benzyl-2,2′-bipyridine,
and 6-benzoyl-2,2′-bipyridine were synthesized, and their acylation
reactions were studied. Acylation of platinum complexes based on 6-(4-R-phenylamino)-2,2′-bipyridine
derivatives (R = CH<sub>3</sub>O, CH<sub>3</sub>, Cl, COOEt) tolerates
both electron-donating and electron-withdrawing substituents on the
aryl ring that are para to the amino group. However, platinum complexes
based on 6-(3-R′-phenylamino)-2,2′-bipyridine (R′
= CH<sub>3</sub>, Cl, Br) did not undergo the acylation reaction under
the same conditions. Interestingly, the acylation of the platinum
complexes based on 6-(3-fluorophenylamino)-2,2′-bipyridine
proceeded smoothly, and the results indicate that the acylation is
regiospecific and occurs at the metalated carbon. Complexes based
on 6-phenoxy-2,2′-bipyridine, 6-phenylthio-2,2′-bipyridine,
and 6-benzyl-2,2′-bipyridine are also regioselectively acylated.
A cyclometalated platinum complex based on 6-benzoyl-2,2′-bipyridine,
where the benzene is more electron deficient than those in other cyclometalated
platinum complexes, failed to undergo the acylation reaction. The
acylation can be carried out in acetic acid, 1,2-dichloroethane, benzonitrile,
and acetonitrile. Other acyl halides such as benzoyl chloride and
crotonyl chloride are also effective acylating reagents. On the basis
of the fact that the reaction is discouraged by the electron deficiency
of the phenyl ring and contrasting results of the acylation of platinum
complexes based on 6-(3-R′-phenylamino)-2,2′-bipyridine
(R′ = CH<sub>3</sub>, F, Cl, Br), an unprecedented electrophilic
addition–platinum migration–rearomatization cascade
mechanism is proposed for the regiospecific acylation reaction
Computational and Experimental Study on Selective sp<sup>2</sup>/sp<sup>3</sup> or Vinylic/Aryl Carbon–Hydrogen Bond Activation by Platinum(II): Geometries and Relative Stability of Isomeric Cycloplatinated Compounds
Cyclometalating
ligands 6-(1-phenylethyl)-2,2′-bipyridine
(<b>L4</b>), 6-(1-phenylvinyl)-2,2′-bipyridine (<b>L5</b>), and 6-(prop-1-en-2-yl)-2,2′-bipyridine (<b>L6</b>) were synthesized by the Negishi coupling of 6-bromo-2,2′-bipyridine
with the corresponding organozinc reagents. The reaction of <b>L4</b> with K<sub>2</sub>PtCl<sub>4</sub> produced only the cycloplatinated
compound <b>4a</b> via sp<sup>2</sup> C–H bond activation.
The reactions of <b>L5</b> and <b>L6</b> produced exclusively
the cycloplatinated compounds <b>5b</b> and <b>6a</b>,
respectively, via vinylic C–H bond activation. DFT calculations
were performed on 12 possible cycloplatination products from the reaction
of <i>N</i>-alkyl-<i>N</i>-phenyl-2,2′-bipyridin-6-amine
(alkyl = methyl (<b>L1</b>), ethyl (<b>L2</b>), and isopropyl
(<b>L3</b>)) and <b>L4</b>–<b>L6</b>. The
results show that compounds <b>1b</b>–<b>3b</b> resulting from the sp<sup>3</sup> C–H bond activation of <b>L1</b>–<b>L3</b> are thermodynamic products, and
their relative stability is attributed to the planar geometry that
allows for a better conjugation. Similar reasoning also applies to
the stability of products from vinylic C–H bond activation
of <b>L5</b> and <b>L6</b>. The relative stability of
isomeric cycloplatinated compounds <b>4a</b> and <b>4b</b> may be due to the different strengths of C–Pt bonds. The
steric interaction is the major cause of severe distortion from a
planar coordination geometry in the cycloplatinated compounds, which
leads to instability of the corresponding cyclometalated products
and a higher kinetic barrier for C–H bond activation
Synthesis, Structure, Photophysics, and a DFT Study of Phosphorescent C*N<sup>∧</sup>N- and C<sup>∧</sup>N<sup>∧</sup>N‑Coordinated Platinum Complexes
The reaction of <i>N</i>,<i>N</i>-diphenyl-2,2′-bipyridin-6-amine (<b>L1</b>) and <i>N</i>,<i>N</i>-diphenyl-6-(1<i>H</i>-pyrazol-1-yl)Âpyridin-2-amine (<b>L2</b>) with K<sub>2</sub>PtCl<sub>4</sub> produced C*N<sup>∧</sup>N-coordinated
cycloplatinated compounds with a five–six fused metallacycle <b>1a</b> and <b>2a</b>, respectively, which were then converted
into their phenylacetylide derivatives <b>1b</b> and <b>2b</b>, respectively. Similar reactions starting from 2-phenyl-6-(1<i>H</i>-pyrazol-1-yl)Âpyridine (<b>L3</b>) produced C<sup>∧</sup>N<sup>∧</sup>N-coordinated platinum complexes <b>3a</b> and <b>3b</b> with a five–five-fused metallacycle.
The structures of <b>1a</b>, <b>1b</b>, <b>2b</b>, <b>3a</b>, and <b>3b</b> were determined by X-ray crystallography.
The C*N<sup>∧</sup>N-coordinated platinum complexes are closer
to a square geometry, whereas the C<sup>∧</sup>N<sup>∧</sup>N-coordinated complexes display a nearly perfect planar geometry.
The π···π interactions were revealed in
the crystal packing for <b>1a</b>, <b>2b</b>, and <b>3a</b> with a π···π contact of 3.450,
3.422, and 3.414 Ã…, respectively. Two conformers were revealed
in the crystal structure of <b>2b</b>, one with the phenyl ring
of the phenylacetylide being approximately parallel with the coordination
plane and the other with the phenyl ring being approximately perpendicular
to the coordination plane. Both <b>1a</b> and <b>1b</b> are weakly emissive in the red region. Complexes <b>2a</b> and <b>3a</b> are also weakly emissive, but their acetylide
derivatives <b>2b</b> and <b>3b</b> emitted strongly green
light at room temperature with quantum yields of 43 and 62%, respectively.
DFT/TDDFT calculations were performed to elucidate the nature of their
electronic transitions. The calculations suggested that lowest singlet
and triplet excited states are characteristic of a mixed state involving
one or more charge-transfer transitions such as ILCT, MLCT, and LLCT
Computational and Experimental Study on Selective sp<sup>2</sup>/sp<sup>3</sup> or Vinylic/Aryl Carbon–Hydrogen Bond Activation by Platinum(II): Geometries and Relative Stability of Isomeric Cycloplatinated Compounds
Cyclometalating
ligands 6-(1-phenylethyl)-2,2′-bipyridine
(<b>L4</b>), 6-(1-phenylvinyl)-2,2′-bipyridine (<b>L5</b>), and 6-(prop-1-en-2-yl)-2,2′-bipyridine (<b>L6</b>) were synthesized by the Negishi coupling of 6-bromo-2,2′-bipyridine
with the corresponding organozinc reagents. The reaction of <b>L4</b> with K<sub>2</sub>PtCl<sub>4</sub> produced only the cycloplatinated
compound <b>4a</b> via sp<sup>2</sup> C–H bond activation.
The reactions of <b>L5</b> and <b>L6</b> produced exclusively
the cycloplatinated compounds <b>5b</b> and <b>6a</b>,
respectively, via vinylic C–H bond activation. DFT calculations
were performed on 12 possible cycloplatination products from the reaction
of <i>N</i>-alkyl-<i>N</i>-phenyl-2,2′-bipyridin-6-amine
(alkyl = methyl (<b>L1</b>), ethyl (<b>L2</b>), and isopropyl
(<b>L3</b>)) and <b>L4</b>–<b>L6</b>. The
results show that compounds <b>1b</b>–<b>3b</b> resulting from the sp<sup>3</sup> C–H bond activation of <b>L1</b>–<b>L3</b> are thermodynamic products, and
their relative stability is attributed to the planar geometry that
allows for a better conjugation. Similar reasoning also applies to
the stability of products from vinylic C–H bond activation
of <b>L5</b> and <b>L6</b>. The relative stability of
isomeric cycloplatinated compounds <b>4a</b> and <b>4b</b> may be due to the different strengths of C–Pt bonds. The
steric interaction is the major cause of severe distortion from a
planar coordination geometry in the cycloplatinated compounds, which
leads to instability of the corresponding cyclometalated products
and a higher kinetic barrier for C–H bond activation
Synthesis, Structure, Photophysics, and a DFT Study of Phosphorescent C*N<sup>∧</sup>N- and C<sup>∧</sup>N<sup>∧</sup>N‑Coordinated Platinum Complexes
The reaction of <i>N</i>,<i>N</i>-diphenyl-2,2′-bipyridin-6-amine (<b>L1</b>) and <i>N</i>,<i>N</i>-diphenyl-6-(1<i>H</i>-pyrazol-1-yl)Âpyridin-2-amine (<b>L2</b>) with K<sub>2</sub>PtCl<sub>4</sub> produced C*N<sup>∧</sup>N-coordinated
cycloplatinated compounds with a five–six fused metallacycle <b>1a</b> and <b>2a</b>, respectively, which were then converted
into their phenylacetylide derivatives <b>1b</b> and <b>2b</b>, respectively. Similar reactions starting from 2-phenyl-6-(1<i>H</i>-pyrazol-1-yl)Âpyridine (<b>L3</b>) produced C<sup>∧</sup>N<sup>∧</sup>N-coordinated platinum complexes <b>3a</b> and <b>3b</b> with a five–five-fused metallacycle.
The structures of <b>1a</b>, <b>1b</b>, <b>2b</b>, <b>3a</b>, and <b>3b</b> were determined by X-ray crystallography.
The C*N<sup>∧</sup>N-coordinated platinum complexes are closer
to a square geometry, whereas the C<sup>∧</sup>N<sup>∧</sup>N-coordinated complexes display a nearly perfect planar geometry.
The π···π interactions were revealed in
the crystal packing for <b>1a</b>, <b>2b</b>, and <b>3a</b> with a π···π contact of 3.450,
3.422, and 3.414 Ã…, respectively. Two conformers were revealed
in the crystal structure of <b>2b</b>, one with the phenyl ring
of the phenylacetylide being approximately parallel with the coordination
plane and the other with the phenyl ring being approximately perpendicular
to the coordination plane. Both <b>1a</b> and <b>1b</b> are weakly emissive in the red region. Complexes <b>2a</b> and <b>3a</b> are also weakly emissive, but their acetylide
derivatives <b>2b</b> and <b>3b</b> emitted strongly green
light at room temperature with quantum yields of 43 and 62%, respectively.
DFT/TDDFT calculations were performed to elucidate the nature of their
electronic transitions. The calculations suggested that lowest singlet
and triplet excited states are characteristic of a mixed state involving
one or more charge-transfer transitions such as ILCT, MLCT, and LLCT
Reaction of <i>N</i>‑Isopropyl‑<i>N</i>‑phenyl-2,2′-bipyridin-6-amine with K<sub>2</sub>PtCl<sub>4</sub>: Selective C–H Bond Activation, C–N Bond Cleavage, and Selective Acylation
The selective C–H bond activation
of <i>N</i>-isopropyl-<i>N</i>-phenyl-2,2′-bipyridin-6-amine
promoted by PtÂ(II)
was complicated by the low selectivity of sp<sup>2</sup> C–H
bond activation in acetonitrile and low yield of sp<sup>3</sup> C–H
activation in acetic acid. The use of a base was found to effectively
suppress the competing sp<sup>3</sup> C–H bond activation in
acetonitrile, improving the selectivity of sp<sup>2</sup> C–H
bond activation from 70% to 99%. In the reaction in acetic acid, the
low yield was due to the competing C–N bond cleavage. The use
of a base reduced the C–N bond cleavage, but not completely.
The reaction of <i>N</i>-<i>tert</i>-butyl-<i>N</i>-phenyl-2,2′-bipyridin-6-amine with K<sub>2</sub>PtCl<sub>4</sub> in acetic acid produced the cyclometalated complex
with complete C–N bond cleavage and its acylated derivative.
These results indicated that the C–N bond cleavage might proceed
via heterolytic C–N bond dissociation. The acylation following
the C–N cleavage in the reaction in acetic acid is regioselective.
Further experiments showed that the reaction of <i>N</i>-phenyl-2,2′-bipyridin-6-amine with K<sub>2</sub>PtCl<sub>4</sub> in acetic acid produced the cyclometalated complex, while
the reaction in a mixture of acetic anhydride and acetic acid produced
the acylated cyclometalated complex. An X-ray crystal structure study
revealed strong intramolecular H bonding in the acylated complexes.
The regioselectivity was explained in terms of H bonding and the electron
distribution predicted by the DFT calculations