Troponate/Aminotroponate Ruthenium-Arene Complexes: Synthesis, Structure, and Ligand-Tuned Mechanistic Pathway for Direct C-H Bond Arylation with Aryl Chlorides in Water
A series of water-soluble troponate/aminotroponate ruthenium(II)-arene complexes were synthesized, where O,O and N,O chelating troponate/aminotroponate ligands stabilized the piano-stool mononuclear ruthenium-arene complexes. Structural identities for two of the representating complexes were also established by single-crystal X-ray diffraction studies. These newly synthesized troponate/aminotroponate ruthenium-arene complexes enable efficient C-H bond arylation of arylpyridine in water. The unique structure-activity relationship in these complexes is the key to achieve efficient direct C-H bond arylation of arylpyridine. Moreover, the steric bulkiness of the carboxylate additives systematically directs the selectivity toward mono- versus diarylation of arylpyridines. Detailed mechanistic studies were performed using mass-spectral studies including identification of several key cyclometalated intermediates. These studies provided strong support for an initial cycloruthenation driven by carbonate-assisted deprotonation of 2-phenylpyridine, where the relative strength of η(6)-arene and the troponate/aminotroponate ligand drives the formation of cyclometalated 2-phenylpyridine Ru-arene species, [(η(6)-arene)Ru(κ(2)-C,N-phenylpyridine) (OH2)](+) by elimination of troponate/aminotroponate ligands and retaining η(6)-arene, while cyclometalated 2-phenylpyridine Ru-troponate/aminotroponate species [(κ (2)-troponate/aminotroponate)Ru(κ(2)-C,N-phenylpyridine)(OH2)2] was generated by decoordination of η(6)-arene ring during initial C-H bond activation of 2-phenylpyridine. Along with the experimental mass-spectral evidence, density functional theory calculation also supports the formation of such species for these complexes. Subsequently, these cycloruthenated products activate aryl chloride by facile oxidative addition to generate C-H arylated products..
Medienart: |
Artikel |
---|
Erscheinungsjahr: |
2016 |
---|---|
Erschienen: |
2016 |
Enthalten in: |
Zur Gesamtaufnahme - volume:55 |
---|---|
Enthalten in: |
Inorganic chemistry - 55(2016), 13, Seite 6739 |
Sprache: |
Englisch |
---|
Beteiligte Personen: |
Dwivedi, Ambikesh D [VerfasserIn] |
---|
Links: |
---|
RVK: |
---|
Förderinstitution / Projekttitel: |
|
---|
PPN (Katalog-ID): |
OLC1979073686 |
---|
LEADER | 01000caa a2200265 4500 | ||
---|---|---|---|
001 | OLC1979073686 | ||
003 | DE-627 | ||
005 | 20230714202759.0 | ||
007 | tu | ||
008 | 160720s2016 xx ||||| 00| ||eng c | ||
028 | 5 | 2 | |a PQ20160720 |
035 | |a (DE-627)OLC1979073686 | ||
035 | |a (DE-599)GBVOLC1979073686 | ||
035 | |a (PRQ)pubmed_primary_273051430 | ||
035 | |a (KEY)0074867620160000055001306739troponateaminotroponaterutheniumarenecomplexessynt | ||
040 | |a DE-627 |b ger |c DE-627 |e rakwb | ||
041 | |a eng | ||
082 | 0 | 4 | |a 540 |q DNB |
084 | |a VA 4680 |q AVZ |2 rvk | ||
100 | 1 | |a Dwivedi, Ambikesh D |e verfasserin |4 aut | |
245 | 1 | 0 | |a Troponate/Aminotroponate Ruthenium-Arene Complexes: Synthesis, Structure, and Ligand-Tuned Mechanistic Pathway for Direct C-H Bond Arylation with Aryl Chlorides in Water |
264 | 1 | |c 2016 | |
336 | |a Text |b txt |2 rdacontent | ||
337 | |a ohne Hilfsmittel zu benutzen |b n |2 rdamedia | ||
338 | |a Band |b nc |2 rdacarrier | ||
520 | |a A series of water-soluble troponate/aminotroponate ruthenium(II)-arene complexes were synthesized, where O,O and N,O chelating troponate/aminotroponate ligands stabilized the piano-stool mononuclear ruthenium-arene complexes. Structural identities for two of the representating complexes were also established by single-crystal X-ray diffraction studies. These newly synthesized troponate/aminotroponate ruthenium-arene complexes enable efficient C-H bond arylation of arylpyridine in water. The unique structure-activity relationship in these complexes is the key to achieve efficient direct C-H bond arylation of arylpyridine. Moreover, the steric bulkiness of the carboxylate additives systematically directs the selectivity toward mono- versus diarylation of arylpyridines. Detailed mechanistic studies were performed using mass-spectral studies including identification of several key cyclometalated intermediates. These studies provided strong support for an initial cycloruthenation driven by carbonate-assisted deprotonation of 2-phenylpyridine, where the relative strength of η(6)-arene and the troponate/aminotroponate ligand drives the formation of cyclometalated 2-phenylpyridine Ru-arene species, [(η(6)-arene)Ru(κ(2)-C,N-phenylpyridine) (OH2)](+) by elimination of troponate/aminotroponate ligands and retaining η(6)-arene, while cyclometalated 2-phenylpyridine Ru-troponate/aminotroponate species [(κ (2)-troponate/aminotroponate)Ru(κ(2)-C,N-phenylpyridine)(OH2)2] was generated by decoordination of η(6)-arene ring during initial C-H bond activation of 2-phenylpyridine. Along with the experimental mass-spectral evidence, density functional theory calculation also supports the formation of such species for these complexes. Subsequently, these cycloruthenated products activate aryl chloride by facile oxidative addition to generate C-H arylated products. | ||
700 | 1 | |a Binnani, Chinky |4 oth | |
700 | 1 | |a Tyagi, Deepika |4 oth | |
700 | 1 | |a Rawat, Kuber S |4 oth | |
700 | 1 | |a Li, Pei-Zhou |4 oth | |
700 | 1 | |a Zhao, Yanli |4 oth | |
700 | 1 | |a Mobin, Shaikh M |4 oth | |
700 | 1 | |a Pathak, Biswarup |4 oth | |
700 | 1 | |a Singh, Sanjay K |4 oth | |
773 | 0 | 8 | |i Enthalten in |t Inorganic chemistry |d Washington, DC [u.a.] : Soc., 1962 |g 55(2016), 13, Seite 6739 |w (DE-627)129095907 |w (DE-600)7558-9 |w (DE-576)014432145 |x 0020-1669 |7 nnns |
773 | 1 | 8 | |g volume:55 |g year:2016 |g number:13 |g pages:6739 |
856 | 4 | 2 | |u http://www.ncbi.nlm.nih.gov/pubmed/27305143 |
912 | |a GBV_USEFLAG_A | ||
912 | |a SYSFLAG_A | ||
912 | |a GBV_OLC | ||
912 | |a SSG-OLC-CHE | ||
912 | |a SSG-OLC-PHA | ||
912 | |a SSG-OLC-DE-84 | ||
912 | |a GBV_ILN_70 | ||
912 | |a GBV_ILN_2006 | ||
912 | |a GBV_ILN_4306 | ||
936 | r | v | |a VA 4680 |
951 | |a AR | ||
952 | |d 55 |j 2016 |e 13 |h 6739 |