PMID- 37018737
OWN - NLM
STAT- PubMed-not-MEDLINE
DCOM- 20230503
LR  - 20230504
IS  - 1879-1123 (Electronic)
IS  - 1044-0305 (Linking)
VI  - 34
IP  - 5
DP  - 2023 May 3
TI  - Investigation of Unusual N-(Triphenyl-lambda(5)-phosphanylidene) Amide Fragmentation 
      Observed upon MS/MS Collision-Induced Dissociation.
PG  - 969-976
LID - 10.1021/jasms.3c00051 [doi]
AB  - A mechanism of unusual tandem (MS/MS) fragmentation of protonated species of 
      N-(triphenyl-lambda(5)-phosphanylidene) derivatives, [M + H](+) to generate 
      triphenylphosphine oxide (TPPO) within the mass spectrometer has been 
      investigated and reported. Collision-induced dissociation of these molecules 
      resulted in the generation of TPPO as a signature fragment. This fragment 
      suggested the presence of a P-O bond in the structure which was contrary to the 
      structure of the compound identified by nuclear magnetic resonance spectrometry 
      (NMR) and single-crystal X-ray diffractometry (SXRD) techniques with a P horizontal lineN bond 
      rather than a P-O bond. In order to confirm the generation of the TPPO fragment 
      within the mass spectrometer, 14 different N-(triphenyl-lambda(5)-phosphanylidene) 
      derivatives containing amide, (18)O-labeled amide, thiamide, and nonacyl 
      phosphazene derivatives were synthesized and their MS/MS behavior was studied by 
      liquid chromatography-high-resolution mass spectrometry. Fragmentation of these 
      amide derivatives generated TPPO/TPPS or their (18)O-labeled analogues as the 
      major fragment in almost all cases under similar MS conditions. Based on the 
      outcome of these experiments, a plausible mechanism for such fragmentation, 
      involving the intramolecular shifting of oxygen from carbon to phosphorus, has 
      been proposed. DFT calculations for the protonated species at 
      B3LYP-D3/6-31+G(d,p) further supported the proposed mechanism involving a 
      four-membered ring, P-O-C-N, as the transition state. Details of this work are 
      presented here.
FAU - Kurmi, Moolchand
AU  - Kurmi M
AD  - Biocon Bristol Myers Squibb Research & Development Centre (BBRC), Syngene 
      International Limited, Bangalore 560099, India.
FAU - Kadambar, Vasantha Krishna
AU  - Kadambar VK
AD  - Biocon Bristol Myers Squibb Research & Development Centre (BBRC), Syngene 
      International Limited, Bangalore 560099, India.
FAU - Srinivas, Pavan
AU  - Srinivas P
AD  - Biocon Bristol Myers Squibb Research & Development Centre (BBRC), Syngene 
      International Limited, Bangalore 560099, India.
FAU - Reddi, Yernaidu
AU  - Reddi Y
AUID- ORCID: 0000-0002-6743-9582
AD  - Biocon Bristol Myers Squibb Research & Development Centre (BBRC), Syngene 
      International Limited, Bangalore 560099, India.
FAU - Panda, Manoranjan
AU  - Panda M
AD  - Biocon Bristol Myers Squibb Research & Development Centre (BBRC), Bristol-Myers 
      Squibb, Bangalore 560099, India.
FAU - Peddicord, Michael
AU  - Peddicord M
AUID- ORCID: 0000-0003-1930-0647
AD  - Bristol Myers Squibb Company, 1 Squibb Drive, New Brunswick, New Jersey 08903, 
      United States.
FAU - Miller, Scott A
AU  - Miller SA
AD  - Bristol Myers Squibb Company, 1 Squibb Drive, New Brunswick, New Jersey 08903, 
      United States.
FAU - Young, Joel
AU  - Young J
AD  - Bristol Myers Squibb Company, 1 Squibb Drive, New Brunswick, New Jersey 08903, 
      United States.
FAU - Bhutani, Hemant
AU  - Bhutani H
AUID- ORCID: 0000-0001-5443-7257
AD  - Biocon Bristol Myers Squibb Research & Development Centre (BBRC), Bristol-Myers 
      Squibb, Bangalore 560099, India.
FAU - Bajpai, Lakshmikant
AU  - Bajpai L
AUID- ORCID: 0000-0002-0513-7888
AD  - Biocon Bristol Myers Squibb Research & Development Centre (BBRC), Bristol-Myers 
      Squibb, Bangalore 560099, India.
LA  - eng
PT  - Journal Article
DEP - 20230405
PL  - United States
TA  - J Am Soc Mass Spectrom
JT  - Journal of the American Society for Mass Spectrometry
JID - 9010412
SB  - IM
EDAT- 2023/04/06 06:00
MHDA- 2023/04/06 06:01
CRDT- 2023/04/05 16:22
PHST- 2023/04/06 06:01 [medline]
PHST- 2023/04/06 06:00 [pubmed]
PHST- 2023/04/05 16:22 [entrez]
AID - 10.1021/jasms.3c00051 [doi]
PST - ppublish
SO  - J Am Soc Mass Spectrom. 2023 May 3;34(5):969-976. doi: 10.1021/jasms.3c00051. 
      Epub 2023 Apr 5.