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Author: Charles Andrew McAuliffe
Publisher: John Wiley & Sons
ISBN:
Category : Science
Languages : en
Pages : 458
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Author: Charles Andrew McAuliffe
Publisher: John Wiley & Sons
ISBN:
Category : Science
Languages : en
Pages : 458
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Author: Samuel O. Grim
Publisher:
ISBN:
Category :
Languages : en
Pages : 43
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The phosphorus-31 nmr spectra of eleven cis and seven trans compounds of the type (R sub n Ph sub 3-n P)2PtCl2, where R = alkyl and n = 1,2, or 3, show that the platinum-195 to phosphorus-31 coupling constant is always larger for the cis compound than for the corresponding trans compound and that the phosphorus chemical shift of the cis compound is upfield from that of the corresponding trans compound. The formation of the tris-phosphine complex by addition of excess tertiary phosphine to the monomer has been demonstrated by conductivity and 31p nmr measurements and confirmed by isolation of the compounds, (MePh2P)3PtCl)Cl and (PrPh2P)3 - PtCl)BPh4. The preparation of several new chlorine bridged dimers is also reported. The phosphorus-31 chemical shifts are reported for twenty-five compounds of the type (RnPh sub 3-nP)M(CO)5, where R is alkyl, n is 0,1,2,3 and M is Cr, Mo, or W. The 183W-31P spin-spin coupling is observed for all the tungsten compounds and a linear correlation exists between these coupling constants and the carbonyl stretching frequencies in the respective compounds. (Author).
Author: Charles Andrew McAuliffe
Publisher:
ISBN: 9781349815609
Category : Antimony compounds
Languages : en
Pages : 0
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Author: R. B. King
Publisher:
ISBN:
Category :
Languages : en
Pages : 33
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The base-catalyzed addition of phosphorus-hydrogen and arsenic-hydrogen bonds to the carbon-carbon multiple bonds in vinylphosphines and ethynylphosphines provides a useful new method for the synthesis of novel polytertiary phosphines and phosphine-arsines. Using this method the authors have prepared in large quantities and studied the coordination chemistry of the tritertiary phosphine ((C6H5)2PCH2CH2)2PC6H5, the two isomeric tetratertiary phosphines (C6H5)2PCH2CH2P(C6H5)CH2CH2P(C6H5)CH2CH2P(C6H5)2 and ((C6H5)2PCH2CH2)3P, and the hexatertiary phosphine ((C6H5)2PCH2CH2)2PCH2CH2P(CH2CH2P(C6H5)2)2. This preparative method also provides convenient syntheses of the mixed phosphine-arsines as (C6H5)2PCH2CH2As(C6H5)2. A similar base-catalyzed addition of (C6H5)2EH (E = P or As) to vinyl isocyanide gives the novel isocyanide derivatives (C6H5)2ECH2CH2NC (E = P or As). However, base-catalyzed addition of C6H5PH2 to vinyl isocyanide results in 1,4-addition to give the new phosphorus-carbon-nitrogen heterocycle 1-phenyl-4,5-dihydro-3-azaphosphole. This report also describes transition metal complexes of the ligands (C6H5)2PCCC6H5, (C6H5)2PCH2CCCH2P(C6H5)2, ((CH3)2N)3E (E = P or As), and (p-(CH3)2NC6H4)nP(C6H5)(3-n) (n =1, 2, and 3). (Author).
Author: Paul S. Pregosin
Publisher: Springer Science & Business Media
ISBN: 3642488307
Category : Science
Languages : en
Pages : 164
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Book Description
For almost a quarter of a century the words "nuclear magnetic reso nance" were synonymous with proton I,leasurements. During this period the literature abounded with a seemingly infinite variety of 1H NHR studies concerned primarily with carbon chemistry. Occasionally a "novel" nucleus was studied and, even in those early days, the poten- 13 14 31 19 tial offered by C, N, P and F was clearly recognized. Despite the allure, the technical difficulties involved in measuring some of these nuclei were far from trivial. Small magnetic moments and low natural abundance in combination with spin-spin coupling from other nuclei, mostly protons, resulted in a signal-to-noise problem whose severity effectively excluded the study of metal complexes with unfa vorable solubility characteristics. The first important breakthrough came with the advent of broad band 1H-decoupling. For example, the featureless broad 31p resonance associated with the commonly used ligand triphenyl phosphine is converted to a sharp, more readily ob served singlet when wide-band decoupling is employed (see Fig. 1). Despite this improvement investigation of more interesting molecules, such as catalytically active complexes was forced to await the devel opment of Fourier Transform methods since only with relatively rapid signal averaging methods could sufficient signal-to-noise ratios be achieved.
Author: Maurizio Peruzzini
Publisher: Springer Science & Business Media
ISBN: 9048138175
Category : Science
Languages : en
Pages : 477
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Book Description
Each chapter of Phosphorus Compounds: Advanced Tools in Catalysis and Material Sciences have been carefully selected by the editors in order to represent a state-of-the-art overview of how phosphorus chemistry can provide solutions in various fields of applications. The editors have assembled an international array of world-renowned scientists and each chapter is written by experts in the fields of synthetic chemistry, homogeneous catalysis, dendrimers, theoretical calculations, materials science, and medicinal chemistry with a special focus on the chemistry of phosphorus compounds. Phosphorus Compounds: Advanced Tools in Catalysis and Material Sciences is of interest to a general readership ranging from advanced university course students to experts in academia and industry.
Author: Hannah Sinclair
Publisher:
ISBN:
Category :
Languages : en
Pages :
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Coordination chemistry usually applies to transition metals, but has recently been extended to the p-block elements. For the pnictogen atoms (group 15), this type of coordination chemistry has already been applied to antimony and bismuth, where they behave as Lewis acceptor centres. However, complexes with nitrogen and phosphorus as Lewis acidic centres are rare, due to their relatively small atomic radii and inherent basic nature. Instead, these elements (Pn(III)) are typically observed as donor centres because they are better at donating their electron pair, than they are at accepting them. To enhance the Lewis acidity at the phosphorus and nitrogen centres, a cationic charge can be introduced by heterolytically abstracting a halide and replacing it with a weakly coordinating anion, providing more opportunities for new reactivity. The presence of a stereochemically active lone pair at the acceptor site also introduces new reactivity patterns to be explored. The formation of these main group coordination complexes opens doors to potential applications in catalysis, small molecule activation, or as material precursors. 2,2'-bipyridine (bipy) has been a prototypical ligand used in transition metal coordination chemistry due to its high basicity and oxidative resistance. This property has been exploited to enable a comprehensive study of a series of Pn(III) tricationic and dicationic complexes using 2,2'-bipyridine (bipy); 4,4'-di-tert-butyl-2,2'-bipyridine (tBu2bipy); 4-dimethylaminopyridine (DMAP); and other main group containing ligands.
Author: Paul C. J. Kamer
Publisher: John Wiley & Sons
ISBN: 1118299701
Category : Technology & Engineering
Languages : en
Pages : 673
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Book Description
Over the last 60 years the increasing knowledge of transition metal chemistry has resulted in an enormous advance of homogeneous catalysis as an essential tool in both academic and industrial fields. Remarkably, phosphorus(III) donor ligands have played an important role in several of the acknowledged catalytic reactions. The positive effects of phosphine ligands in transition metal homogeneous catalysis have contributed largely to the evolution of the field into an indispensable tool in organic synthesis and the industrial production of chemicals. This book aims to address the design and synthesis of a comprehensive compilation of P(III) ligands for homogeneous catalysis. It not only focuses on the well-known traditional ligands that have been explored by catalysis researchers, but also includes promising ligand types that have traditionally been ignored mainly because of their challenging synthesis. Topics covered include ligand effects in homogeneous catalysis and rational catalyst design, P-stereogenic ligands, calixarenes, supramolecular approaches, solid phase synthesis, biological approaches, and solubility and separation. Ligand families covered in this book include phosphine, diphosphine, phosphite, diphosphite, phosphoramidite, phosphonite, phosphinite, phosphole, phosphinine, phosphinidenene, phosphaalkenes, phosphaalkynes, P-chiral ligands, and cage ligands. Each ligand class is accompanied by detailed and reliable synthetic procedures. Often the rate limiting step in the application of ligands in catalysis is the synthesis of the ligands themselves, which can often be very challenging and time consuming. This book will provide helpful advice as to the accessibility of ligands as well as their synthesis, thereby allowing researchers to make a more informed choice. Phosphorus(III) Ligands in Homogeneous Catalysis: Design and Synthesis is an essential overview of this important class of catalysts for academic and industrial researchers working in catalyst development, organometallic and synthetic chemistry.
Author: Jean-Pierre Majoral
Publisher: Springer
ISBN: 3540457313
Category : Science
Languages : en
Pages : 250
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Book Description
Undoubtedly the chemistry of phosphorus appears more and more attractive in the sense that phosphorus presents an extraordinary versatile behaviour that allows the synthesis of a large number of different phosphorus reagents usable for applications in different fields, from biology to material science without f- getting key applications in catalysis. The full maturity of this topic of research can be explained by all the acquired knowledge over these twenty last years. Organic and inorganic chemistries of P , P and P species have been the s- in ]V v ject of thousands of publications while the chemistry of low coordinated ph- phorus derivatives experienced its hour of glory from the 1970s to the early 1990s. In parallel, interactions between phosphorus compounds and transition metals afforded many complexes, a lot of which present fascinating properties as catalysts. The interest in all these themes really is not decreasing, indeed some fas- nating areas of research are emerging or are the subject of many investigations: the medicinal chemistry of bisphosphonates, the role of phosphorus in biology, phosphorus ligands in radiopharmaceutical chemistry, phosphorus in material science, new polymers and dendrimers incorporating phosphorus, and as- metric catalysis to name but a few. Indeed researchers, benefitting from their background in basic phosphorus chemistry are developing many new fields of research.
Author: Edward Joseph Lukosius
Publisher:
ISBN:
Category : Transition metal compounds
Languages : en
Pages : 268
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Book Description
