PMID- 33252161
OWN - NLM
STAT- PubMed-not-MEDLINE
LR  - 20210203
IS  - 1439-7641 (Electronic)
IS  - 1439-4235 (Linking)
VI  - 22
IP  - 3
DP  - 2021 Feb 3
TI  - Interplay of Huckel and Mobius Aromaticity in Metal-Metal Quintuple Bonded 
      Complexes of Cr, Mo, and W with Amidinate Ligand: Ab initio DFT and 
      Multireference Analysis*.
PG  - 298-311
LID - 10.1002/cphc.202000923 [doi]
AB  - The aromaticity of metal-metal quintuple bonded complexes of the type M(2) L(2) 
      (M=Cr, Mo, and W; L=amidinate) are studied employing gauge including magnetically 
      induced ring current (GIMIC) analysis and electron density of delocalized bonds 
      (EDDB). It is found that the complexes possess two types of aromaticity: i) 
      Huckel aromaticity through delocalization of ligand pi electrons with metal-metal 
      delta-bond-forming 6 conjugated electrons (4pi and 2delta) ring; ii) Craig-Mobius 
      aromaticity through delocalization of pi electrons of both the ligands with metal 
      d-orbitals in Craig type orientation forming 10pi electrons ring with a double 
      twist. Extended transition state natural orbital chemical valence (ETS-NOCV) and 
      canonical molecular orbital natural chemical shielding (CMO-NCS) analysis confirm 
      the Craig-Mobius type arrangement of the orbitals. Furthermore, the unprecedented 
      Huckel and Mobius type aromaticity is confirmed from the plot of the current 
      pathways using 3D line integral convolution (3D-LIC) plots. The metal-metal bond 
      order also increases down the group as justified from the complete active space 
      self-consistent field (CASSCF) analysis. Due to an increase in the pi and delta 
      electron conjugation, both the Huckel and Mobius aromaticity increase down the 
      group.
CI  - (c) 2020 Wiley-VCH GmbH.
FAU - Patra, Shanti G
AU  - Patra SG
AUID- ORCID: 0000-0003-3084-1495
AD  - Department of Chemical Sciences, Ariel University, Ariel, 40700, Israel.
FAU - Mondal, Totan
AU  - Mondal T
AUID- ORCID: 0000-0002-5590-8839
AD  - Department of Organic Chemistry and the, Lise Meitner-Minerva Centre for 
      Computational Quantum Chemistry, The Hebrew University, Jerusalem, 91904, Israel.
LA  - eng
PT  - Journal Article
DEP - 20201230
PL  - Germany
TA  - Chemphyschem
JT  - Chemphyschem : a European journal of chemical physics and physical chemistry
JID - 100954211
SB  - IM
OTO - NOTNLM
OT  - CASSCF
OT  - aromaticity
OT  - density functional calculations
OT  - magnetically induced ring current analysis
OT  - metal-metal quintuple bond
EDAT- 2020/12/01 06:00
MHDA- 2020/12/01 06:01
CRDT- 2020/11/30 08:46
PHST- 2020/11/07 00:00 [received]
PHST- 2020/11/29 00:00 [revised]
PHST- 2020/12/01 06:00 [pubmed]
PHST- 2020/12/01 06:01 [medline]
PHST- 2020/11/30 08:46 [entrez]
AID - 10.1002/cphc.202000923 [doi]
PST - ppublish
SO  - Chemphyschem. 2021 Feb 3;22(3):298-311. doi: 10.1002/cphc.202000923. Epub 2020 
      Dec 30.