PMID- 31909598
OWN - NLM
STAT- PubMed-not-MEDLINE
DCOM- 20200123
LR  - 20200123
IS  - 1520-510X (Electronic)
IS  - 0020-1669 (Linking)
VI  - 59
IP  - 2
DP  - 2020 Jan 21
TI  - Diverse Functionalization of Ruthenium-Chelated 2-Picolylamines: Oxygenation, 
      Dehydrogenation, Cyclization, and N-Dealkylation.
PG  - 1355-1363
LID - 10.1021/acs.inorgchem.9b03065 [doi]
AB  - "Chemical noninnocence" of metal-coordinated 2-picolylamine (PA) derivatives has 
      been introduced upon its reaction with the metal precursor 
      [Ru(II)(Cl)(H)(CO)(PPh(3))(3)] under basic conditions. This in effect leads to 
      the facile formation of metalated amide, imine, ring-cyclized pyrrole, and an 
      N-dealkylated congener based on the fine-tuning of an amine nitrogen (N(amine)) 
      and a methylene center (C(alpha)) at the PA backbone. It develops oxygenated L1' in 1 
      and cyclized L4' in 4 upon switching of the N(amine) substituent of PA from aryl 
      to an electrophilic pent-3-en-2-one moiety. On the other hand, imposing the 
      substituent at the C(alpha) position of PA modifies its reactivity profile, leading 
      to a dehydrogenation (2/3) or N-dealkylation (6) process. The divergent 
      reactivity profile of metalated PA is considered to proceed through a common 
      dianionic intermediate. Further, a competitive scenario of C-H bond 
      functionalization of coordinated PA versus the ligand-exchange process has been 
      exemplified in the presence of external electrophile such as benzyl bromide or 
      methylene iodide. Authentication of the product formation as well as elucidation 
      of the reaction pathway has been addressed by their crystal structures and 
      spectroscopic features in conjunction with the transition-state (TS) theory.
FAU - Panda, Sanjib
AU  - Panda S
AD  - Department of Chemistry , Indian Institute of Technology (IIT) Bombay , Powai , 
      Mumbai 400076 , India.
FAU - Singha Hazari, Arijit
AU  - Singha Hazari A
AD  - Department of Chemistry , Indian Institute of Technology (IIT) Bombay , Powai , 
      Mumbai 400076 , India.
FAU - Gogia, Manish
AU  - Gogia M
AD  - Department of Chemistry , Indian Institute of Technology (IIT) Bombay , Powai , 
      Mumbai 400076 , India.
FAU - Lahiri, Goutam Kumar
AU  - Lahiri GK
AUID- ORCID: 0000-0002-0199-6132
AD  - Department of Chemistry , Indian Institute of Technology (IIT) Bombay , Powai , 
      Mumbai 400076 , India.
LA  - eng
PT  - Journal Article
DEP - 20200107
PL  - United States
TA  - Inorg Chem
JT  - Inorganic chemistry
JID - 0366543
SB  - IM
EDAT- 2020/01/08 06:00
MHDA- 2020/01/08 06:01
CRDT- 2020/01/08 06:00
PHST- 2020/01/08 06:00 [pubmed]
PHST- 2020/01/08 06:01 [medline]
PHST- 2020/01/08 06:00 [entrez]
AID - 10.1021/acs.inorgchem.9b03065 [doi]
PST - ppublish
SO  - Inorg Chem. 2020 Jan 21;59(2):1355-1363. doi: 10.1021/acs.inorgchem.9b03065. Epub 
      2020 Jan 7.