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Low Spin Pseudotetrahedral Cobalt Tris(phosphino)borate Complexes

Citation

Jenkins, David Matthew (2005) Low Spin Pseudotetrahedral Cobalt Tris(phosphino)borate Complexes. Dissertation (Ph.D.), California Institute of Technology. http://resolver.caltech.edu/CaltechETD:etd-02102005-144940

Abstract

A synthetic protocol is developed for the preparation of a thallium complex featuring the tris(phosphino)borate ligand [PhBP3] ([PhBP3] = [PhB(CH2PPh2)3]-). The transmetallating reagent, [PhBP3]Tl, is characterized by single crystal X-ray diffraction and solution NMR spectroscopy, and is the first example of a stable homoleptic Tl(I)-phosphine complex.

The synthesis and characterization of [PhBP3]Co-X (X = I, Br or Cl) is discussed. These halide complexes are structurally characterized and magnetic investigations establish that they are low spin when monomeric. The low spin iodide complex is a monomer in solution and in the solid state. The other halides exhibit a monomer/dimer equilibrium that complicates their magnetic behavior. Theoretical calculations help provide a rationale as to why these pseudotetrahedral species are low spin. A classic high spin species supported by [PhBP3] is compared to the low spin complexes.

Spin state control involving pseudotetrahedral [PhBP3]Co(II) complexes is explored. Both high and low spin, as well as spin crossover, complexes are synthesized and structurally characterized. The complexes are discussed in terms of the relationship between local geometry and spin state. Changing the axial or tripodal ligand can cause a different spin state to be favored. Since the energy difference between the states is small, ligand changes at remote positions from the metal center have a significant effect on spin crossover phenomena. Theoretical calculations help illuminate why the low spin state is preferred for many of the complexes.

The first examples of cobalt imide complexes ([PhBP3]Co≡NR (R = aryl or alkyl)) are prepared and they are supported by the [PhBP3] ligand. These diamagnetic species are evaluated by NMR and single crystal X-ray diffraction. Theoretical studies suggest that they have a similar molecular orbital bonding scheme as the previously prepared group 9 imides.

A cobalt μ2-bridging nitride complex (([PhBP3]Co)2(μ-N)) is synthesized and structurally characterized. This mixed-valence species is evaluated by magnetometry to determine its ground state, which is low spin (S = ½).

Several cobalt diazoalkane complexes are prepared. These diamagnetic species adopt two different bonding modes depending on the nature of the diazoalkane ligand.

Item Type:Thesis (Dissertation (Ph.D.))
Subject Keywords:imide; imido; low spin; nitride; pseudotetrahedral
Degree Grantor:California Institute of Technology
Division:Chemistry and Chemical Engineering
Major Option:Chemistry
Thesis Availability:Public (worldwide access)
Research Advisor(s):
  • Peters, Jonas C.
Thesis Committee:
  • Gray, Harry B. (chair)
  • MacMillan, David W. C.
  • Bercaw, John E.
  • Peters, Jonas C.
Defense Date:31 January 2005
Record Number:CaltechETD:etd-02102005-144940
Persistent URL:http://resolver.caltech.edu/CaltechETD:etd-02102005-144940
Related URLs:
URLURL TypeDescription
https://doi.org/10.1039/B104447HDOIArticle adapted for Ch. 2
https://doi.org/10.1021/ja026433eDOIArticle adapted for Ch. 3
https://doi.org/10.1021/ja036198fDOIArticle adapted for Ch. 4
https://doi.org/10.1021/ja026852bDOIArticle adapted for Ch. 5 and 7
Default Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:591
Collection:CaltechTHESIS
Deposited By: Imported from ETD-db
Deposited On:14 Feb 2005
Last Modified:28 Sep 2017 15:39

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PDF (Full thesis) - Final Version
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PDF (Chapter 0: Introductory material) - Final Version
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PDF (Chapter 1: Background and introduction to cobalt tris(phosphino)borate chemistry) - Final Version
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PDF (Chapter 2: A homoleptic phosphine adduct of Tl(I)) - Final Version
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PDF (Chapter 3: Elucidation of a low spin cobalt(II) system in a distorted tetrahedral geometry) - Final Version
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PDF (Chapter 4: Spin state tuning at pseudotetrahedral d7 ions: examining the structural and magnetic phenomena of 4-coordinate [BP3]CoII-X systems) - Final Version
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PDF (Chapter 5: Synthesis of cobalt imide complexes) - Final Version
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PDF (Chapter 6: A structurally characterized homobimetallic bridging μ2-nitride complex of cobalt) - Final Version
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PDF (Chapter 7: Diazoalkane complexes of cobalt) - Final Version
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