Small Molecule Activation and Coordination Chemistry of Bismuth, f-Element, and Alkaline Earth ...

220 Pages·2014·7.91 MB·English

UC Irvine
UC Irvine Electronic Theses and Dissertations
Title
Small Molecule Activation and Coordination Chemistry of Bismuth, f-Element, and Alkaline
Earth Complexes
Permalink
https://escholarship.org/uc/item/41h3t519
Author
Kindra, Douglas
Publication Date
2014

Peer reviewed|Thesis/dissertation
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University of California
UNIVERSITY OF CALIFORNIA,
IRVINE

Small Molecule Activation and Coordination Chemistry of Bismuth, f-Element,
and Alkaline Earth Complexes

DISSERTATION

Submitted in partial satisfaction of the requirements
for the degree of

DOCTOR OF PHILOSOPHY

in Chemistry

By

Douglas R. Kindra

Dissertation Committee:
Professor William J. Evans, Chair
Professor Andrew S. Borovik
Professor Alan F. Heyduk

2014
Chapter 2 © 2013 American Chemical Society
Chapter 3 © 2014 The Royal Society of Chemistry
Chapter 4 © 2014 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Chapter 7 © 2014 American Chemical Society
Chapter 8 © 2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Chapter 8 © 2012 American Chemical Society

All other materials © 2014 Douglas R. Kindra
Dedication

This dissertation is dedicated to my loving wife Lindsay, who encouraged me to pursue my goals
with enthusiasm, as long as I was home from lab by midnight.

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Table of Contents
Page
LIST OF FIGURES v
LIST OF TABLES ix
LIST OF COMPOUNDS xii
ACKNOWLEDGMENTS xiv
CURRICULUM VITAE svi
ABSTRACT OF DISSERTATION xviii
INTRODUCTION 1
CHAPTER 1: Synthesis and Structure of Bis- and Tris-Benzyl Bismuth 17
Complexes
CHAPTER 2: Insertion of CO and COS into Bi−C Bonds: Reactivity of a 27
2
Bismuth NCN Pincer Complex of an Oxyaryl Dianionic
Ligand, [2,6-(Me NCH ) C H ]Bi(C H tBu O)
2 2 2 6 3 6 2 2
CHAPTER 3: Bismuth-Based Cyclic Synthesis of 3,5-Di-tert-butyl-4- 66
hydroxybenzoic Acid via the Oxyarylcarboxy Dianion,
(O CC H tBu O)2−
2 6 2 2
CHAPTER 4: Nitric Oxide Insertion Reactivity with the Bismuth–Carbon 80
Bond: Formation of the Oximate Anion,
[ON=(C H tBu O)]1−, from the Oxyaryl Dianion,
6 2 2
(C H tBu O)2−
6 2 2
CHAPTER 5: Bismuth in Tri- and Polydentate Nitrogen Coordination 100
Environments with H–Bond Acceptors: Isolation of an
Empty Cavity Metal Complex and a Polymetallic Cluster
iii
CHAPTER 6: Facile Transfer of the Dianionic Oxyarylcarboxy Ligand, 111
[O C(C H tBu -3,5-O-4)]2−, from Bismuth to Uranium:
2 6 2 2
Isolation and Characterization of
(C Me ) U(Cl)[O C(C H tBu -3-5-OH-4)]
5 5 2 2 6 2 2
CHAPTER 7: Magnetic Susceptibility of Uranium Complexes 125
CHAPTER 8: Samarium Metallocene Chemistry in Carbon Dioxide 141
Activation and Reductive Carbon-Carbon Coupling
APPENDIX A: Synthesis, Characterization, and Reduction Chemistry of 161
Alkaline Earth Metallocenes
APPENDIX B: Room Temperature and Low Temperature Magnetic Data of 175
U3+, U4+ and U5+ ions.

iv
List of Figures
Page
Figure 0.1 ORTEP representation of [2,6-(Me NCH ) C H ]BiCl showing the ψ- 7
2 2 2 6 3 2
octahedral geometry often times seen in B3+ complexes.
Figure 0.2 Bond distances of the oxyaryl dianionic ligand of compound 1 and the 11
monoanionic phenyl ligand of [1-H][BPh ].
4
Figure 1.1 ORTEP representation of Ar′Bi(η1-CH Ph) , Bn-2, with thermal 19
2 2
ellipsoids drawn at the 50% probability level. Hydrogen atoms are
omitted for clarity. Only a dashed line is drawn between Bi1 and N1
because the distance is 3.058(4) Å.
Figure 1.2 ORTEP representation of Bi(η1-CH Ph) , Bn-3, with thermal ellipsoids 21
2 3
drawn at the 50% probability level. Hydrogen atoms omitted for
clarity.
Figure 2.1 ORTEP representation of Ar′Bi[O C(C H tBu -3-5-O-4)-κ2O,O′], 2, 29
2 6 2 2
from two perspectives, with thermal ellipsoids drawn at the 50%
probability level. Hydrogen atoms are omitted for clarity.
Figure 2.2 ORTEP representation of Ar′Bi[OSC(C H tBu -3-5-O-4)-κ2O,S], 3, 30
6 2 2
from two perspectives, with thermal ellipsoids drawn at the 50%
probability level. Hydrogen atoms are omitted for clarity.
Figure 2.3 Bond distances in the oxyaryl, oxyarylcarboxy, and oxyarylthiocarboxy 30
dianionic ligands of compounds 1, 2, and 3 and the normal bond
lengths of the closely related monoanionic hydroxyaryl ligand in [1-
H][BPh ].
4
Figure 2.4 ORTEP representation of {Ar′Bi[O C(C H tBu -3-5-OH-4)- 34
2 6 2 2
κ2O,O′]}[BF ], [2-H][BF ], with thermal ellipsoids drawn at the 50%
4 4
probability level. Hydrogen atoms are omitted for clarity.
v
Figure 2.5 Bond distances in the oxyaryl and oxyarylcarboxy dianionic ligands of 35
compounds 1 and 2 compared to the normal bond lengths of the closely
related monoanionic carboxylate ligand in [2-H][BF ].
4
Figure 2.6 From left to right, HOMO of compounds 1, 2 and 3. All orbitals are 36
drawn with a contour value of 0.05.
Figure 2.7 ORTEP representation of [Ar′Bi(C H tBu -3,5-OSiMe -4)][CF SO ], 39
6 2 2 3 3 3
6, with thermal ellipsoids drawn at the 50% probability level.
Hydrogen atoms are omitted for clarity.
Figure 2.8 ORTEP representation of Ar′Bi(CN)(C H tBu -3,5-OSiMe -4), 7, with 40
6 2 2 3
thermal ellipsoids drawn at the 50% probability level. Hydrogen atoms
are omitted for clarity.
Figure 2.9 ORTEP representation of Ar′Bi(N ) , 9, with thermal ellipsoids drawn 41
3 2
at the 50% probability level. Hydrogen atoms are omitted for clarity.
Figure 3.1 1H NMR spectrum of compound 2 and 1 equiv of [Et NH][Cl] in 70
3
acetonitrile-d showing evidence for the proposed intermediate
3
Ar′Bi(Cl)[O C(C H tBu -3-5-OH-4)].
2 6 2 2
Figure 3.2 ORTEP representation of both linkage isomers of 71
Ar′Bi[O C(C H tBu -3-5-OH-4)] , 11, drawn at the 50% probability
2 6 2 2 2
level. Hydrogen atoms are omitted for clarity.
Figure 4.1 ORTEP representation of [Ar′Bi(ONC H -3,5-tBu -4-O)] (μ-O), 13, 82
6 2 2 2
from two perspectives, with thermal ellipsoids drawn at the 50%
probability level. Hydrogen atoms are omited for clarity. The two
bismuth centers are bound by a bridging oxygen (O1).
Figure 4.2 ORTEP representation of Ar′Bi(ONC H -3,5-tBu -4-O) , 14, with 83
6 2 2 2
thermal ellipsoids drawn at 50% probability level. Hydrogen atoms are
omitted for clarity.
vi
Figure 4.3 ORTEP representation of (Ph CS)(Ar′)Bi(ONC H -3,5-tBu -4-O), 15, 87
3 6 2 2
from two perspectives, with thermal ellipsoids drawn at the 50%
probability level. Hydrogen atoms are omitted for clarity.
Figure 4.4 Bond distances in the oximate ligands of compounds 13, 14, and 15 89
compared to the dianionic oxyaryl and oxyarylcarboxy ligands in 1 and
2, respectively. Compounds containing two oximate ligands (13 and
14) list both distances for each bond.
Figure 4.5 UV-vis of compound 13 in THF (black), DCM (red), Et O (green), 91
2
MeCN (blue) and toluene (orange). In only THF and MeCN is the
second absorption at ca. 600 nm present.
Figure 5.1 ORTEP representation of Bi[MST], 16, drawn at the 50% probability 102
level. Hydrogen atoms and solvent molecules are omitted for clarity.
Figure 5.2 (A) Voltammogram of Bi[MST], 16 (B) voltammogram of Al[MST] 104
control. All CV performed in DMSO vs ferrocene/ferrocenium with
0.1 M of [Bu N][PF ].
4 6
Figure 5.3 ORTEP representation of Bi Na O [TSB] , 17, drawn at the 50% 106
5 2 5 5
probability level. Hydrogen atoms and solvent molecules are omitted
for clarity. The coordination environment for Bi2, Bi3, Bi4, and Bi5
are shown.
Figure 5.4 Coordination environment for Bi1 in compound 17, and surrounding 107
bismuth and sodium metal centers.
Figure 6.1 ORTEP representation of (C Me ) U(Cl)[O C(C H tBu -3-5-OH-4)], 116
5 5 2 2 6 2 2
18, with thermal ellipsoids drawn at the 50% probability level.
Hydrogen atoms are omitted for clarity.
Figure 7.1 Histogram of the uranium magnetic moments for monometallic 128
complexes of the three common oxidation states with U3+, U4+, and U5+
in black, grey, and white, respectively. Histogram bin widths are 0.20
µ .
B
vii
Figure 7.2 Room temperature magnetic moments of monometallic U3+ (top, 129
green), U4+ (middle, orange), and U5+ (bottom, blue) complexes in µ .
B
Histogram bin widths of 0.20, y-axis are not to scale.
Figure 7.3 Low temperature (1.8 – 5 K) magnetic moments (µ ) of monometallic 130
B
U3+ (top, green), U4+ (middle, orange), and U5+ (bottom, blue)
complexes in µ . Histogram bin widths of 0.20, y-axis are not to scale.
B
Figure 7.4 Examples of μ versus temperature plots for a series of related 133
B
(AdArO) tacn complexes from Meyer and co-workers:6 (A) U3+
3
complexes [((t-BuArO) tacn)U], (1), [((AdArO) tacn)U], (1-Ad), and [((t-
3 3
BuArO) tacn)U(NCCMe ], (4); (B) U4+ complexes
3 3
[((AdArO) tacn)U(N )], (U(IV)-N3), [((AdArO) tacn)U(Cl)], (U(IV)-
3 3 3
Cl), [((AdArO) tacn)U(Br)], (U(IV)-Br), and [((AdArO) tacn)U(I)],
3 3
(U(IV)-I); (C) the U5+ complex [((AdArO) tacn)U(NSi(CH ) )].
3 3 3
Reprinted with permission from Chemical Communications 2006,
1353.
Figure 8.1 ORTEP representation of [(C Me ) Sm(THF)] (μ-κ1:κ2-CO ), 20, 145
5 5 2 2 3
drawn at the 50% probability level. Hydrogen atoms are omitted for
clarity.
Figure 8.2 ORTEP representation of [(C Me ) Sm(C H N)] (µ-C H N ), 21, 149
5 5 2 5 5 2 10 8 2
drawn at 50% probability level. Hydrogen atoms and co-crystallized
solvent molecules omitted for clarity.
Figure 8.3 ORTEP representation of [(C Me ) Sm] (µ-ƞ2:ƞ2-BuC Bu), 22, drawn 152
5 5 2 2 4
at 25% probability level. Hydrogen atoms are omitted for clarity.
Figure A.1 X-band EPR spectra of a 5:1 THF:Et O solution of 25-Ba at a) 293 K 165
2
and b) 77 K.
Figure A.2 UV-vis spectra of 25-Ba in THF showing decomposition over 2 hours. 166
A new spectra was collected every 15 min.
Figure A.3 X-band EPR spectra of a 5:1 THF:Et O solution of the dark 169
2
green/yellow reaction mixture from Scheme 1 at a) 293 K and b) 77 K.
viii