Synthesis Structure And Reactivity Of Polynuclear Group Vi Metal Complexes

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Synthesis Structure And Reactivity Of Polynuclear Group Vi Metal Complexes

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Author : David Owen Marler
language : en
Publisher:
Release Date : 1984

Synthesis Structure And Reactivity Of Polynuclear Group Vi Metal Complexes written by David Owen Marler and has been published by this book supported file pdf, txt, epub, kindle and other format this book has been release on 1984 with Transition metal compounds categories.

Synthesis Structure And Reactivity Of Polynuclear Transition Metal Complexes

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Author : Oi Mi Lacy
language : en
Publisher:
Release Date : 1985

Synthesis Structure And Reactivity Of Polynuclear Transition Metal Complexes written by Oi Mi Lacy and has been published by this book supported file pdf, txt, epub, kindle and other format this book has been release on 1985 with categories.

Metal Pyrrolide Complexes In Three Fold Symmetry

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Author : William Hill Harman
language : en
Publisher:
Release Date : 2010

Metal Pyrrolide Complexes In Three Fold Symmetry written by William Hill Harman and has been published by this book supported file pdf, txt, epub, kindle and other format this book has been release on 2010 with categories.

Given the prominence of six-coordinate pseudo-octahedral complexes in transition metal chemistry, lower coordinate complexes in tetrahedral, trigonal pyramidal and trigonal bipyramidal configurations have garnered increased interest due to the changes in electronic structure and reactivity resultant from three-fold symmetry relative to the four-fold symmetry commonly observed in their pseudo-octahedral counterparts. Herein, we report a range of such effects in a collection of transition metal complexes supported by chelating, trianionic trispyrrolide ligands [tpaR]3-. In chapter one, two trigonal pyramidal iron(II) complexes, [(tpaPh)Fe]- and [(tpaMes)Fe]-, are discussed which are capable of undergoing oxygen atom transfer reactions and subsequent activation of strong C-H bonds. Additionally, the mesityl derivative is capable of oxygen atom transfer from nitrous oxide, an attractive but notoriously unreactive molecule. In chapter two, this family of iron(II) complexes is expanded to include tert-butyl, 2,4,6-triisopropylphenyl and 2,6-difluorophenyl substituted variants, and the magnetic properties of this homologous series of trigonal pyramidal iron(II) complexes are explored. Notably, a number of these complexes exhibit frequency dependent signals at low temperature in the imaginary component of ac magnetic susceptibility measurements performed in the presence of a small applied field. Further exploration of this behavior via magnetometry, high-field EPR and Mössbauer spectroscopy reveal a large barrier to magnetic relaxation in these complexes, in some cases comparable to the best known single molecule magnets. This phenomenon is accounted for by the unquenched orbital angular momentum present in a three-fold symmetric high spin d6 system, leading to significant uniaxial anisotropy and a barrier to spin inversion. Progress towards a magneto-structural analysis of this behavior is made for this series. Chapter three contains a through treatment of the coordination, redox and group transfer chemistry of the iron(II) platform [(tpaMes)Fe]-. In particular, it is shown that this complex is capable of supporting both high and low spin five coordinate adducts, including a rare example of a paramagnetic carbonyl complex of iron(II), [(tpaMes)Fe(CO)]-. Furthermore, the redox chemistry of this system is illustrated in the synthesis of the neutral iron(III) complex (tpaMes)Fe(i-PrNH2). As an extensiont to the oxygen atom chemistry presented in chapter one, nitrene group transfer to [(tpaMes)Fe]- is described, resulting in the synthesis of an iron(III) amido complex. The identity of this species is confirmed by high resolution electrospray mass spectrometry as well as Mössbauer, x-ray absorption and EPR spectroscopies. In chapter four, the vanadium chemistry of [tpaR]3- is introduced. In particular, the vanadium(III) complex (tpaMes)V(THF) is show to react with an aryl azide to yield an isolable vanadium(V) diazenylimido species, a member of a very rare structural type. This complex is shown to decompose unimolecularly by dinitrogen loss to generate the cooresponding vanadium(V) imido. In addition to the vanadium-nitrogen multiple bond chemistry described, the synthesis two pseudo-three-fold symmetric vanadium(IV) oxo species is discussed. Single crystal x-ray structures of both complexes reveal a distorted coordination geometry and a short vanadium-oxo distance, consistent with a triple bond. The oxidation of both of these complexes to the corresponding vanadium(V) oxo is performed and shown by x-ray crystallography to result in the relief of the distortion observed in the vanadium(IV) oxo complexes. Taken together, these results shed light on the nature of metal ligand multiple bonding in three-fold symmetric geometries. Chapter five discusses the chromium complexes of [tpaMes]3-, in particular the group transfer and redox chemistry of the system. Both chromium(II) and chromium(III) complexes are available by direct metallation, and the chromium(II) complex [(tpaMes)Cr(DME)]- is shown to undergo both oxygen atom and nitrene group transfer reactions to yield chromium(IV) oxo and imido complexes respectively. The chromium(IV) imido complex exhibits rich redox chemistry, and its oxidation to the isostructural chromium(V) and chromium(VI) complexes are demonstrated.

Synthesis Structure And Reactivity Of Group 13 Diketiminate Complexes

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Author : Baixin Qian
language : en
Publisher:
Release Date : 1999

Synthesis Structure And Reactivity Of Group 13 Diketiminate Complexes written by Baixin Qian and has been published by this book supported file pdf, txt, epub, kindle and other format this book has been release on 1999 with Aluminum compounds categories.

Synthesis Structures And Reactions Of Polynuclear Metal Complexes With Unsaturated Carboxylic Acids

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Author : I. Little
language : en
Publisher:
Release Date : 1986

Synthesis Structures And Reactions Of Polynuclear Metal Complexes With Unsaturated Carboxylic Acids written by I. Little and has been published by this book supported file pdf, txt, epub, kindle and other format this book has been release on 1986 with categories.

The Synthesis And Reactivity Of Di And Polynuclear Mixed Metal Complexes

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Author : C. Marsden
language : en
Publisher:
Release Date : 1985

The Synthesis And Reactivity Of Di And Polynuclear Mixed Metal Complexes written by C. Marsden and has been published by this book supported file pdf, txt, epub, kindle and other format this book has been release on 1985 with categories.

Synthesis Structure And Reactivity Of Transition Metal Complexes Containing P O And N Donor Ligands

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Author : Vladimir F. Kuznetsov
language : en
Publisher:
Release Date : 2001

Synthesis Structure And Reactivity Of Transition Metal Complexes Containing P O And N Donor Ligands written by Vladimir F. Kuznetsov and has been published by this book supported file pdf, txt, epub, kindle and other format this book has been release on 2001 with Catalysis categories.

Synthesis And Characterization Of Novel Polynuclear Group 6 Carbonyl Anionic Complexes Obtained By Ligand Exchange Reactions

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Author : Rafael A. Adrian
language : en
Publisher:
Release Date : 2004

Synthesis And Characterization Of Novel Polynuclear Group 6 Carbonyl Anionic Complexes Obtained By Ligand Exchange Reactions written by Rafael A. Adrian and has been published by this book supported file pdf, txt, epub, kindle and other format this book has been release on 2004 with Ligands categories.

Synthesis And Characterization Of Group Vi Metal Complexes For Non Classical Oxygenation Reactions

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Author : Leila Amery Galang Ranis
language : en
Publisher:
Release Date : 2014

Synthesis And Characterization Of Group Vi Metal Complexes For Non Classical Oxygenation Reactions written by Leila Amery Galang Ranis and has been published by this book supported file pdf, txt, epub, kindle and other format this book has been release on 2014 with categories.

Synthesis And Reactivity Of Main Group Complexes For Applications In Small Molecule Activation

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Author : Minh Tho Nguyen
language : en
Publisher:
Release Date : 2019

Synthesis And Reactivity Of Main Group Complexes For Applications In Small Molecule Activation written by Minh Tho Nguyen and has been published by this book supported file pdf, txt, epub, kindle and other format this book has been release on 2019 with categories.

The work described in this thesis is focused on the preparation of a series of novel main group complexes, featuring unusual structural and bonding situations, and the study of their reactivity toward small molecules. The new zinc complexes dimphZnBu (V-2) and dimphZnCl2Li(THF)3 (V-3), supported by a diiminophenyl (dimph) ligand were prepared. The reaction of complex V-3 with LiHBEt3 resulted in hydride transfer to the C=N imine group to give an unusual zinc dimer (V-7). The latter transformation occurs via formation of compound (ɳ1(C),ĸ1(N)- 2,6-(2,6-iPr2C6H3N=CH)2C6H3)2Zn (V-5) which can be also accessed by reduction of V-7 with KC8. Diiminophenyl (dimph) proved to be an excellent ligand platform to stabilise a low-valent phosphorus centre. The resultant compound dimphP (VI-2), which can be rationalised as an imino-stabilised phosphinidene or benzoazaphopshole, shows remarkable chemical stability toward water and oxygen. VI-2 reacts with excess strong acid HCl to generate the P(III) chloride (dimHph)PCl (VI-6). Surprisingly, substitution of the chloride under some nucleophilic (KOBut) and electrophilic conditions (Me3SiOTf) regenerates the parent compound VI-2 by proton removal from the weakly acidic CH2N position. A related species (dimH2ph)P (VI-10) is produced upon thermal rearrangement of the hydride (dimHph)PH (VI-9). The molecular structure and reactivity of compounds VI-2 and other related compounds are also discussed. The reduction of the O,C,O-chelated phosphorus (III) chloride (VI-16) ( O,C,O = 2,6-bis[(2,6-diisopropyl)phenoxyl]phenyl) with KC8 or PMe3 resulted in the formation of a cyclic three-membered phosphorus compound (VI-18). The intermediacy of phosphinidene VI-17 was confirmed by trapping experiments and a VT 31P{1H} NMR study. The reaction of in-situ generated phosphinidene with either PhSiH3 or HBpin resulted in the formation of an unprecedented phosphine (VI-23). The treatment of VI-16 with two equivalents of DippNHC carbene led to ArP(Cl)NHC product (VI-24). The germylone dimNHCGe (dimNHC = diimino N-Heterocyclic Carbene, VII-8) was successfully prepared by the reduction of germanium cation (VII-7) with KC8. The molecular structure of VII-8 was unambiguously established, using NMR spectroscopy and single-crystal X-ray diffraction analysis. The reactivity of VII-8 was investigated. VII-8 is inactive towards butadiene but undergoes an oxidative cyclization with tetrachloro-o-benzoquinone to give a tetragermanium derivative. VII-8 undergoes oxidation addition of CH3I and PhI, followed by an unusual migration of the Me and Ph groups from germanium to the carbene ligand. Related chemistry takes place upon protonation with dry HCl, which results in the migration of the hydride to the carbene ligand.