Coordination Chemistry of New Ferrocenyl Phosphane Ligands and Novel N-heterocyclic Carbene Ligand Precursors Containing Cyclopentadienyl Or Fluorenyl Derivatives PDF Download
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Author: Simon Turberville
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Category : Ferrocene
Languages : en
Pages : 0
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Author: Simon Turberville
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ISBN:
Category : Ferrocene
Languages : en
Pages : 0
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Category : Dissertations, Academic
Languages : en
Pages : 318
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Author: Bryan Kenneth Shaw
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Category :
Languages : en
Pages :
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Author: Emma Karen Bullough
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Category :
Languages : en
Pages : 0
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Author: Tongxun Guo
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ISBN: 9783954049998
Category :
Languages : en
Pages : 185
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Author: Pengfei Ai
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Category :
Languages : en
Pages : 0
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The purpose of this work was the synthesis of N,N'-diphosphanyl-functionalized NHC ligands andtheir coordination chemistry. The novel stable and rigid tridentate N,N'-diphosphanyl-imidazol-2-ylidene was synthesized and experimental and computational information on its stability weregained. It served as a unique platform for the synthesis of novel mono-, di-, tri-, penta-, hexanuclear complexes with the coinage metals (Cu, Ag and Au), exhibiting rare structural features. The mono- and dinuclear complexes with one or two dangling P-donors provided rational access to heterotrinuclear complexes. All these coinage metal complexes have short metal-metalseparations, indicating the presence of d10-d10 interactions, and display excellent luminescentproperties. Partial or complete transmetallation of the homotrinuclear Cu or Ag complexes withPd(0) precursors led to hetero-trinuclear complexes with d10-d10 interactions. In addition to itsbridging behavior, this ligand also showed its chelating behavior in Pd or Cr(III) complexes. Thelatter displayed superior performance in ethylene oligomerization than the Cr(II) complexes andgave mostly oligomers.
Author: Mary Cecilia Johnson
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Category :
Languages : en
Pages : 0
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A novel bis-(protic N-heterocyclic carbene, PNHC) phosphine ligand platform is explored to understand its role in CO2 hydrogenation catalysis and as a supporting scaffold for bimetallic complexes. Optimized syntheses for the bis-(PNHC) phosphine ligand and its metalation with a Ru(II) metal center, as well as the synthesis and coordination chemistry of a library of complexes with varying ancillary ligands (2,2’-bipyridine, 4,4’-dibromo-2,2’-bipyridine, 4,4’-dimethoxy-2,2’-bipyridine, and bis-(diphenylphosphino)ethane) are shown. We describe the hydrogenation of CO2 to formate catalyzed by a Ru(II) bis-(protic N-heterocyclic carbene, p-NHC) phosphine complex [Ru(bpy)(MeCN)(PPh(p-NHC)2)](PF6)2 (1). Under catalytic conditions (20 [micromole] catalyst, 20 bar CO2, 60 bar H2, 5 mL THF, 140 °C, 16 hrs) the activity of 1 is limited only by the amount of K3PO4 present in the reaction, yielding a nearly one to one ratio of turn over number (TON) to equivalents of K3PO4 (relative to 1), with the highest TON = 8,040. Additionally, analysis of the reaction solution post-run reveals the catalyst intact with no free ligand observed. Stoichiometric studies, including examination of unique carbamate and hydride complexes as relevant intermediates, were carried out to probe the operative mechanism and understand the importance of metal-ligand cooperativity in this system. We also describe the synthesis and characterization of [Ru(bpy)(solvent)(P(Ph)(NHC)2-K2-N,N'-M(solvent)2)]2+ (M = Co(II), Zn(II)) and subsequent reactivity with hydroxide and formate. Facile inter- and intramolecular cooperation is observed and the structurally responsive NHC-Cobalt-NHC binding pocket is investigated.
Author: Jordan Holmes
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ISBN:
Category :
Languages : en
Pages : 394
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Category :
Languages : en
Pages : 287
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Author: Leon Xuetong Sun
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Category :
Languages : en
Pages :
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