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Title: Adaptable ligand donor strength: tracking transannular bond interactions in tris(2-pyridylmethyl)-azaphosphatrane (TPAP)

Abstract

Flexible ligands that can adapt their donor strength have enabled unique reactivity in a wide range of inorganic complexes. Most examples are composed of flexible multi-dentate ligands containing a donor that can vary its interaction through its distance to the metal center. We describe an alternative type of adaptable ligand interaction in the neutral multi-dentate ligand tris(2-pyridylmethyl)-azaphosphatrane (TPAP), which contains a proazaphosphatrane unit. Prozaphosphatranes are intrinsically strong phosphorus donors; upon coordination to more Lewis acidic atoms the phosphorus can accept additional electron density from a tertiary nitrogen to form a transannular bond, increasing its donor strength. An experimental and computational investigation of the varying degree of transannular interaction in TPAP when coordinated to late transition metals is reported in this paper. The synthesis and characterization of the complexes M(TPAP), where M = Co(I)Cl, Ni(0)(1,5-cyclooctadiene), Ni(II)(CH3CN)(BF4)2, Pd(II)(CH3CN)(BF4)2, or Pt(II)Cl(PF6) is described. Structural characterization and density functional theory calculation of these complexes, along with the previously reported [Co(II)(TPAP)(CH3CN)](BF4)2 establish significant increases in the degree of transannular interaction of the proazaphosphatrane unit when coordinated to more electron deficient metal ions.

Authors:
ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1];  [2];  [1]; ORCiD logo [1]
  1. Univ. of California, Irvine, CA (United States)
  2. Univ. of Minnesota, Minneapolis, MN (United States)
Publication Date:
Research Org.:
Univ. of California, Irvine, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1611734
Alternate Identifier(s):
OSTI ID: 1473721
Grant/Contract Number:  
SC0012150
Resource Type:
Accepted Manuscript
Journal Name:
Dalton Transactions
Additional Journal Information:
Journal Volume: 47; Journal Issue: 39; Journal ID: ISSN 1477-9226
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Chemistry

Citation Formats

Thammavongsy, Zachary, Cunningham, Drew W., Sutthirat, Natwara, Eisenhart, Reed J., Ziller, Joseph W., and Yang, Jenny Y. Adaptable ligand donor strength: tracking transannular bond interactions in tris(2-pyridylmethyl)-azaphosphatrane (TPAP). United States: N. p., 2018. Web. doi:10.1039/c8dt03180k.
Thammavongsy, Zachary, Cunningham, Drew W., Sutthirat, Natwara, Eisenhart, Reed J., Ziller, Joseph W., & Yang, Jenny Y. Adaptable ligand donor strength: tracking transannular bond interactions in tris(2-pyridylmethyl)-azaphosphatrane (TPAP). United States. https://doi.org/10.1039/c8dt03180k
Thammavongsy, Zachary, Cunningham, Drew W., Sutthirat, Natwara, Eisenhart, Reed J., Ziller, Joseph W., and Yang, Jenny Y. Fri . "Adaptable ligand donor strength: tracking transannular bond interactions in tris(2-pyridylmethyl)-azaphosphatrane (TPAP)". United States. https://doi.org/10.1039/c8dt03180k. https://www.osti.gov/servlets/purl/1611734.
@article{osti_1611734,
title = {Adaptable ligand donor strength: tracking transannular bond interactions in tris(2-pyridylmethyl)-azaphosphatrane (TPAP)},
author = {Thammavongsy, Zachary and Cunningham, Drew W. and Sutthirat, Natwara and Eisenhart, Reed J. and Ziller, Joseph W. and Yang, Jenny Y.},
abstractNote = {Flexible ligands that can adapt their donor strength have enabled unique reactivity in a wide range of inorganic complexes. Most examples are composed of flexible multi-dentate ligands containing a donor that can vary its interaction through its distance to the metal center. We describe an alternative type of adaptable ligand interaction in the neutral multi-dentate ligand tris(2-pyridylmethyl)-azaphosphatrane (TPAP), which contains a proazaphosphatrane unit. Prozaphosphatranes are intrinsically strong phosphorus donors; upon coordination to more Lewis acidic atoms the phosphorus can accept additional electron density from a tertiary nitrogen to form a transannular bond, increasing its donor strength. An experimental and computational investigation of the varying degree of transannular interaction in TPAP when coordinated to late transition metals is reported in this paper. The synthesis and characterization of the complexes M(TPAP), where M = Co(I)Cl, Ni(0)(1,5-cyclooctadiene), Ni(II)(CH3CN)(BF4)2, Pd(II)(CH3CN)(BF4)2, or Pt(II)Cl(PF6) is described. Structural characterization and density functional theory calculation of these complexes, along with the previously reported [Co(II)(TPAP)(CH3CN)](BF4)2 establish significant increases in the degree of transannular interaction of the proazaphosphatrane unit when coordinated to more electron deficient metal ions.},
doi = {10.1039/c8dt03180k},
journal = {Dalton Transactions},
number = 39,
volume = 47,
place = {United States},
year = {Fri Sep 14 00:00:00 EDT 2018},
month = {Fri Sep 14 00:00:00 EDT 2018}
}

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