15 research outputs found
Cyclometalated Iridium Complexes from Intramolecular C–H Activation of [IrCp*Cl{C(OMe)CHC(CH<sub>3</sub>)R}L] (R = CH<sub>3</sub>, Ph; L = PPh<sub>2</sub>Me, PMe<sub>3</sub>)
The (methoxy)alkenylcarbeneiridium
complexes [IrCp*Cl{C(OMe)CHCR<sup>1</sup>R<sup>2</sup>}L]PF<sub>6</sub> (R<sup>1</sup> = CH<sub>3</sub>, R<sup>2</sup> =
CH<sub>3</sub>, Ph; R<sup>1</sup> = Ph, R<sup>2</sup>= H; L = PPh<sub>2</sub>Me, PMe<sub>3</sub>) can undergo an intramolecular C–H
activation of one of the substituents R of the alkenyl fragment to
give new five-membered-ring cyclometalated iridium complexes. In this
work it is shown that the arrangement of substituents in the alkenyl
fragment determines the size of the ring in the iridacycle complexes.
The iridacyclopenta-1,3-diene complexes [IrCp*{C(OMe)CHCRCH<sub>2</sub>}L]PF<sub>6</sub> (L = PPh<sub>2</sub>Me, R = CH<sub>3</sub> (<b>2a</b>), Ph (<b>4a</b>); L
= PMe<sub>3</sub>, R = CH<sub>3</sub> (<b>2b</b>), Ph (<b>4b</b>)) can be deprotonated to give the iridacyclopenta-2,4-diene
complexes [IrCp*{C(OMe)CHCRCH}L]
(L = PPh<sub>2</sub>Me, R = CH<sub>3</sub> (<b>6a</b>), Ph (<b>7a</b>); L = PMe<sub>3</sub>, R = CH<sub>3</sub> (<b>6b</b>), Ph (<b>7b</b>))
Cyclometalated Iridium Complexes from Intramolecular C–H Activation of [IrCp*Cl{C(OMe)CHC(CH<sub>3</sub>)R}L] (R = CH<sub>3</sub>, Ph; L = PPh<sub>2</sub>Me, PMe<sub>3</sub>)
The (methoxy)alkenylcarbeneiridium
complexes [IrCp*Cl{C(OMe)CHCR<sup>1</sup>R<sup>2</sup>}L]PF<sub>6</sub> (R<sup>1</sup> = CH<sub>3</sub>, R<sup>2</sup> =
CH<sub>3</sub>, Ph; R<sup>1</sup> = Ph, R<sup>2</sup>= H; L = PPh<sub>2</sub>Me, PMe<sub>3</sub>) can undergo an intramolecular C–H
activation of one of the substituents R of the alkenyl fragment to
give new five-membered-ring cyclometalated iridium complexes. In this
work it is shown that the arrangement of substituents in the alkenyl
fragment determines the size of the ring in the iridacycle complexes.
The iridacyclopenta-1,3-diene complexes [IrCp*{C(OMe)CHCRCH<sub>2</sub>}L]PF<sub>6</sub> (L = PPh<sub>2</sub>Me, R = CH<sub>3</sub> (<b>2a</b>), Ph (<b>4a</b>); L
= PMe<sub>3</sub>, R = CH<sub>3</sub> (<b>2b</b>), Ph (<b>4b</b>)) can be deprotonated to give the iridacyclopenta-2,4-diene
complexes [IrCp*{C(OMe)CHCRCH}L]
(L = PPh<sub>2</sub>Me, R = CH<sub>3</sub> (<b>6a</b>), Ph (<b>7a</b>); L = PMe<sub>3</sub>, R = CH<sub>3</sub> (<b>6b</b>), Ph (<b>7b</b>))
Nucleophilic Attack in Methoxycarbenes: Heterolytic Cleavage of the Carbon (sp<sup>3</sup>)–Oxygen Bond versus Aminolysis
The
iridium methoxycarbene [IrCp*Cl{C(OMe)CHCPh<sub>2</sub>}(PPh<sub>2</sub>Me)]PF<sub>6</sub> (<b>3</b>) can undergo
a clean attack by nucleophiles at least by two different pathways:
(1) an unusual nucleophilic attack of primary, secondary, and tertiary
amines at the sp<sup>3</sup> carbon–oxygen bond, which gives
an acyl complex and amine alkylation and (2) a nucleophilic attack
of the ammonia at the carbenic carbon, which forms a primary aminocarbene
Formation of Indanone from an Iridanaphthalene Complex
The
first example of evolution of an iridanaphthalene into an indanone
through an intermediate indenyl is reported, serving as a good example
of starting material to obtain indanones. Two new iridanaphthalenes
are obtained by intramolecular C–H activation of a phenyl ring
of a carbene ligand in [IrCp*{C(OMe)CHCPh<sub>2</sub>}(L)]PF<sub>6</sub> (L = PPh<sub>2</sub>Me, PMe<sub>3</sub>) complexes.
It is demonstrated that these iridanaphthalene complexes can undergo
a thermal reaction to give indenyl complexes and 3-phenylindanone
Formation of Indanone from an Iridanaphthalene Complex
The
first example of evolution of an iridanaphthalene into an indanone
through an intermediate indenyl is reported, serving as a good example
of starting material to obtain indanones. Two new iridanaphthalenes
are obtained by intramolecular C–H activation of a phenyl ring
of a carbene ligand in [IrCp*{C(OMe)CHCPh<sub>2</sub>}(L)]PF<sub>6</sub> (L = PPh<sub>2</sub>Me, PMe<sub>3</sub>) complexes.
It is demonstrated that these iridanaphthalene complexes can undergo
a thermal reaction to give indenyl complexes and 3-phenylindanone
Formation of Indanone from an Iridanaphthalene Complex
The
first example of evolution of an iridanaphthalene into an indanone
through an intermediate indenyl is reported, serving as a good example
of starting material to obtain indanones. Two new iridanaphthalenes
are obtained by intramolecular C–H activation of a phenyl ring
of a carbene ligand in [IrCp*{C(OMe)CHCPh<sub>2</sub>}(L)]PF<sub>6</sub> (L = PPh<sub>2</sub>Me, PMe<sub>3</sub>) complexes.
It is demonstrated that these iridanaphthalene complexes can undergo
a thermal reaction to give indenyl complexes and 3-phenylindanone
Nucleophilic Attack in Methoxycarbenes: Heterolytic Cleavage of the Carbon (sp<sup>3</sup>)–Oxygen Bond versus Aminolysis
The
iridium methoxycarbene [IrCp*Cl{C(OMe)CHCPh<sub>2</sub>}(PPh<sub>2</sub>Me)]PF<sub>6</sub> (<b>3</b>) can undergo
a clean attack by nucleophiles at least by two different pathways:
(1) an unusual nucleophilic attack of primary, secondary, and tertiary
amines at the sp<sup>3</sup> carbon–oxygen bond, which gives
an acyl complex and amine alkylation and (2) a nucleophilic attack
of the ammonia at the carbenic carbon, which forms a primary aminocarbene
Formation of Indanone from an Iridanaphthalene Complex
The
first example of evolution of an iridanaphthalene into an indanone
through an intermediate indenyl is reported, serving as a good example
of starting material to obtain indanones. Two new iridanaphthalenes
are obtained by intramolecular C–H activation of a phenyl ring
of a carbene ligand in [IrCp*{C(OMe)CHCPh<sub>2</sub>}(L)]PF<sub>6</sub> (L = PPh<sub>2</sub>Me, PMe<sub>3</sub>) complexes.
It is demonstrated that these iridanaphthalene complexes can undergo
a thermal reaction to give indenyl complexes and 3-phenylindanone
Nucleophilic Attack in Methoxycarbenes: Heterolytic Cleavage of the Carbon (sp<sup>3</sup>)–Oxygen Bond versus Aminolysis
The
iridium methoxycarbene [IrCp*Cl{C(OMe)CHCPh<sub>2</sub>}(PPh<sub>2</sub>Me)]PF<sub>6</sub> (<b>3</b>) can undergo
a clean attack by nucleophiles at least by two different pathways:
(1) an unusual nucleophilic attack of primary, secondary, and tertiary
amines at the sp<sup>3</sup> carbon–oxygen bond, which gives
an acyl complex and amine alkylation and (2) a nucleophilic attack
of the ammonia at the carbenic carbon, which forms a primary aminocarbene