ferrocenyl boronate
National Institutes of Health
Papers overview
Semantic Scholar uses AI to extract papers important to this topic.
[2-(phosphinomethyl)ferrocenyl]diphenylphosphine 2, is an air stable primary phosphine bearing a 1,2-disubstituted ferrocene…
The reaction of FcC≡C–C≡CFc (Fc = Fe(η5-C5H4)(η5-C5H5)) (1) with Co(η5-C5H5)(CO)2 (2) afforded ferrocenyl-functionalized…
The clinical success of cisplatin and its derivatives for the treatment of different cancers has had a profound effect on the use…
Four ferrocene derivative complexes, designated as compound A, B, C, and D (Ferrocenyl)1,3-dimethyl-1,3dione di-aqua cobalt (II…
......................................................................................................................................... ii Preface ........................................................................................................................................... iv Table of contents ............................................................................................................................v List of tables.................................................................................................................................. ix List of figures .................................................................................................................................. x List of schemes ............................................................................................................................ xiv List of symbols .......................................................................................................................... xviii List of abbreviations .................................................................................................................. xix List of new compounds ................................................................................................................ xx Acknowledgements .................................................................................................................. xxiv Foreward ..................................................................................................................................... xxv 1 Early transition metal hydrides and ligand design ..................................................................1 1.1
Early transition metal hydrides .......................................................................................... 1 1.1.1
Overview ..................................................................................................................... 1 1.1.2
Scandium and yttrium hydride complexes .................................................................. 2 1.1.3
Zirconium and hafnium hydride complexes ............................................................. 12 1.2
Phosphinoamide ligands .................................................................................................. 18 1.2.1
Ligand design in the Fryzuk group ........................................................................... 18 1.2.2
Introduction to phosphinoamides .............................................................................. 20 1.2.3
Mononuclear transition metal phosphinoamide complexes ...................................... 24 1.2.4
Multimetallic phosphinoamide complexes ............................................................... 26 vi 1.3
Scope of thesis ................................................................................................................. 30 2 Phosphinoamide scandium and yttrium organometallic complexes ....................................32 2.1
Introduction ...................................................................................................................... 32 2.2
Phosphinoamide supported scandium and yttrium organometallics ................................ 34 2.2.1
Alkane-elimination route to scandium and yttrium complexes ................................ 34 2.2.2
Trisubstituted phosphinoamide scandium and yttrium complexes ........................... 35 2.2.3
Mixed alkyl-phosphinoamide complexes of scandium and yttrium ......................... 38 2.3
Ferrocene-linked phosphinoamides as supporting ligands for scandium ........................ 44 2.3.1
Ferrocene as a diamine linker in ligand design ......................................................... 44 2.3.2
Synthesis of a ferrocenyl diphosphinoamine ............................................................ 45 2.3.3
Synthesis of a ferrocenyl phosphinoamide scandium alkyl complex ....................... 46 2.3.4
Synthesis of a discandium dihydride complex .......................................................... 51 2.4
Conclusion ....................................................................................................................... 56 3 Tri(phosphinoamide) complexes of zirconium .......................................................................58 3.1
Introduction ...................................................................................................................... 58 3.2
Synthesis of phosphinoamide zirconium complexes ....................................................... 61 3.3
Synthesis of organometallic tri(phosphinoamide) zirconium complexes ........................ 67 3.4
Attempted hydrogenolysis of zirconium alkyls ............................................................... 70 3.5
Alternative approaches to hydride complexes ................................................................. 71 3.6
Synthesis of a zirconium phosphide complex .................................................................. 74 3.7
Conclusion ....................................................................................................................... 79 4 Ferrocene-linked phosphinoamide complexes of zirconium .................................................80 4.1
Introduction ...................................................................................................................... 80 vii 4.2
Synthetic route to ferrocenyl diphosphinoamide zirconium complexes .......................... 83 4.3
Synthesis of organometallic zirconium complexes .......................................................... 89 4.3.1
Synthesis and characterization of primary alkyl zirconium complexes .................... 89 4.3.2
Benzyl bonding modes in zirconium complexes ...................................................... 92 4.3.3
Attempted hydrogenolysis of dialkyl zirconium complexes .................................... 93 4.3.4
Synthesis of a zirconium complex containing β-hydrogens ..................................... 93 4.4
Isocyanide insertion reactivity with dialkyl zirconium complexes .................................. 97 4.4.1
Synthesis of iminoacyl complexes ............................................................................ 97 4.4.2
Isomerization from iminoacyl to an amido-alkene complex .................................. 100 4.5
Conclusions .................................................................................................................... 103 5 Electrochemistry of ferrocenyl diphosphinoamide complexes ...........................................105 5.1
Introduction .................................................................................................................... 105 5.2
Introduction to cyclic voltammetry ................................................................................ 106 5.3
Redox behavior in ferrocene-linked diphosphinoamide complexes .............................. 109 5.3.1
Redox behavior of fc(NPPr2)2H2 ............................................................................ 109 5.3.2
Redox behavior of fc(NPPr2)2Sc(CH2SiMe3)(THF) .............................................. 110 5.3.3
Redox behavior of fc(NPPr2)2ZrX2 (X = NMe2, CH2Ph) ...................................... 112 5.3.4
Synthesis and redox behavior of fc(NPPr2)2Li2 ..................................................... 114 5.3.5
Attempted synthetic strategies ................................................................................ 116 5.4
Conclusions .................................................................................................................... 117 6 Diversions and future directions............................................................................................118 6.1
Diversions with porphyrin-supported tantalum complexes ........................................... 118 6.2
Future work on tantalum porphyrin complexes ............................................................. 119 viii 6.3
Diversions synthesizing phosphine-bridged amidate ligands ........................................ 120 6.4
Alteration of the ferrocenyl diphosphinoamide ligand system ...................................... 122 6.4.1
Overview ................................................................................................................. 124 7 Experimental ...........................................................................................................................125 7.1
General procedures ........................................................................................................ 125 7.1.1
Laboratory equipment and procedures .................................................................... 125 7.1.2
Solvents ................................................................................................................... 125 7.1.3
Materials ................................................................................................................. 125 7.1.4
Instrumentation and methods of analysis ................................................................ 126 7.2
Synthesis of compounds ................................................................................................ 129 7.2.1
Complexes pertaining to Chapter 2 ......................................................................... 129 7.2.2
Complexes pertaining to Chapter 3 ......................................................................... 135 7.2.3
Complexes pertaining to Chapter 4 ......................................................................... 141 7.2.4
Complexes pertaining to Chapter 5 ..............................................................
The effects of ferrocenyl chalcones including 1-acetyl-1′-(m-methoxy-p-hydroxycinnamoyl)ferrocene (AVF), 1,1′-di(m-methoxy-p…
Iridium complexes with bidentate P,N ligands represent a class of catalysts that significantly expand the application range of…
These systems were designed in order to modulate the electrochemical and optical properties of the polycyclic moieties by the…
We report a set of novel receptors with the structural feature of having an naphthyl-, pyrenyl-or ferrocenyl subunits, directly…
m-Aminophenylboronate-substituted agarose binds specifically RNA chains carrying a mature 5' cap. The binding occurs most…