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Elusive hypervalent phosphorusπ interactions: evidence for paradigm transformation from hydrogen to phosphorus bonding at low temperatures.
Phys Chem Chem Phys 2019; 21(23):12250-12264PC

Abstract

The π electron systems are the conventional electron donors to the hydrogen acceptors in hydrogen bonding. Apart from the hydrogen atom, halogens, chalcogens, pnicogens and triel/tetrel atoms can also be envisaged as electron acceptors involving π clouds. Markedly, in pnicogenπ interactions, the bonding of the hypervalent (predominantly pentavalent) state of the phosphorus atom with π electron donors is elusive and can be thought of as an intuitive extension to trivalent phosphorusπ interactions. In this work, on the one hand, POCl3 was taken as a prototypical molecule to explore these pentavalent phosphorus interactions and on the other hand, acetylene (C2H2), ethylene (C2H4) and benzene (C6H6), in which phosphorusπ bonding can be expected to compete with hydrogen and halogen bonding interactions, were taken as π electron donors. All three POCl3-C2H2, POCl3-C2H4 and POCl3-C6H6 heterodimers were experimentally generated at low temperatures in Ar and N2 matrices and were characterized by both infrared spectroscopy and state-of-the-art quantum chemical computations. Though hydrogen bonding dominates in POCl3-C2H2 and POCl3-C2H4 heterodimers, phosphorus bonding plays a definite and non-trivial role in their overall stabilization. An interesting paradigm transformation was noticed in the POCl3-C6H6 system, where pentavalent phosphorusπ bonding was observed to completely influence the hydrogen bonding interaction. To further shed light on these Pπ systems, the interaction characteristics were analyzed with the help of electrostatic potential mapping, natural bond orbital and energy decomposition analyses.

Authors+Show Affiliations

Materials Chemistry and Metal Fuel Cycle Group, Homi Bhabha National Institute, Indira Gandhi Centre for Atomic Research, Kalpakkam-603 102, India. nram@igcar.gov.in sundar@igcar.gov.in.Materials Chemistry and Metal Fuel Cycle Group, Homi Bhabha National Institute, Indira Gandhi Centre for Atomic Research, Kalpakkam-603 102, India. nram@igcar.gov.in sundar@igcar.gov.in.Materials Chemistry and Metal Fuel Cycle Group, Homi Bhabha National Institute, Indira Gandhi Centre for Atomic Research, Kalpakkam-603 102, India. nram@igcar.gov.in sundar@igcar.gov.in.Materials Chemistry and Metal Fuel Cycle Group, Homi Bhabha National Institute, Indira Gandhi Centre for Atomic Research, Kalpakkam-603 102, India. nram@igcar.gov.in sundar@igcar.gov.in.

Pub Type(s)

Journal Article

Language

eng

PubMed ID

31139812

Citation

Sruthi, P K., et al. "Elusive Hypervalent Phosphorusπ Interactions: Evidence for Paradigm Transformation From Hydrogen to Phosphorus Bonding at Low Temperatures." Physical Chemistry Chemical Physics : PCCP, vol. 21, no. 23, 2019, pp. 12250-12264.
Sruthi PK, Sarkar S, Ramanathan N, et al. Elusive hypervalent phosphorusπ interactions: evidence for paradigm transformation from hydrogen to phosphorus bonding at low temperatures. Phys Chem Chem Phys. 2019;21(23):12250-12264.
Sruthi, P. K., Sarkar, S., Ramanathan, N., & Sundararajan, K. (2019). Elusive hypervalent phosphorusπ interactions: evidence for paradigm transformation from hydrogen to phosphorus bonding at low temperatures. Physical Chemistry Chemical Physics : PCCP, 21(23), pp. 12250-12264. doi:10.1039/c9cp01925a.
Sruthi PK, et al. Elusive Hypervalent Phosphorusπ Interactions: Evidence for Paradigm Transformation From Hydrogen to Phosphorus Bonding at Low Temperatures. Phys Chem Chem Phys. 2019 Jun 21;21(23):12250-12264. PubMed PMID: 31139812.
* Article titles in AMA citation format should be in sentence-case
TY - JOUR T1 - Elusive hypervalent phosphorusπ interactions: evidence for paradigm transformation from hydrogen to phosphorus bonding at low temperatures. AU - Sruthi,P K, AU - Sarkar,Shubhra, AU - Ramanathan,N, AU - Sundararajan,K, Y1 - 2019/05/29/ PY - 2019/5/30/pubmed PY - 2019/5/30/medline PY - 2019/5/30/entrez SP - 12250 EP - 12264 JF - Physical chemistry chemical physics : PCCP JO - Phys Chem Chem Phys VL - 21 IS - 23 N2 - The π electron systems are the conventional electron donors to the hydrogen acceptors in hydrogen bonding. Apart from the hydrogen atom, halogens, chalcogens, pnicogens and triel/tetrel atoms can also be envisaged as electron acceptors involving π clouds. Markedly, in pnicogenπ interactions, the bonding of the hypervalent (predominantly pentavalent) state of the phosphorus atom with π electron donors is elusive and can be thought of as an intuitive extension to trivalent phosphorusπ interactions. In this work, on the one hand, POCl3 was taken as a prototypical molecule to explore these pentavalent phosphorus interactions and on the other hand, acetylene (C2H2), ethylene (C2H4) and benzene (C6H6), in which phosphorusπ bonding can be expected to compete with hydrogen and halogen bonding interactions, were taken as π electron donors. All three POCl3-C2H2, POCl3-C2H4 and POCl3-C6H6 heterodimers were experimentally generated at low temperatures in Ar and N2 matrices and were characterized by both infrared spectroscopy and state-of-the-art quantum chemical computations. Though hydrogen bonding dominates in POCl3-C2H2 and POCl3-C2H4 heterodimers, phosphorus bonding plays a definite and non-trivial role in their overall stabilization. An interesting paradigm transformation was noticed in the POCl3-C6H6 system, where pentavalent phosphorusπ bonding was observed to completely influence the hydrogen bonding interaction. To further shed light on these Pπ systems, the interaction characteristics were analyzed with the help of electrostatic potential mapping, natural bond orbital and energy decomposition analyses. SN - 1463-9084 UR - https://www.unboundmedicine.com/medline/citation/31139812/Elusive_hypervalent_phosphorusπ_interactions:_evidence_for_paradigm_transformation_from_hydrogen_to_phosphorus_bonding_at_low_temperatures L2 - https://doi.org/10.1039/c9cp01925a DB - PRIME DP - Unbound Medicine ER -