Synthesis and Reactivity of Imido and Oxo Complexes of Transition Metals PDF Download
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Languages : en
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Refer to the Full-Text, p.16-18.
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Languages : en
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Refer to the Full-Text, p.16-18.
Author: Jonathan Paul Mitchell
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Category :
Languages : en
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Author: Jonathan Paul Mitchell
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Category :
Languages : en
Pages : 0
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Category :
Languages : en
Pages : 8
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The synthesis and reactions of late-transition-metal oxo and imido complexes was explored. The deprotonation of platinum(II) hydroxo complexes yielded new oxo complexes. Attempted deprotonation of Cp*Rh(III) hydroxo complexes did not give oxo complexes but complex mixtures probably resulting from reduction of the Rh(III) center. The reaction of Na/Hg with (Cp*RhCl2)2 gave the very reactive Rh(II) dimer, (Cp*RhCl)2. Rhodium(I) imido complexes with the bis(dimethylphosphino)methane ligand were prepared and found to be similar to the previously prepared bis(diphenylphosphino)methane complexes. Attempts to prepare bis(diphenylphosphino)methylamine, bis(diphenylphosphino)phenylamine, PMe{sub e} and NO analogues were not successful. Attempts to prepare Cp*Rh(III) imido complexes resulted in amido complexes and reduction. Rhodium (III) tris(3.5-dimethylpyrazoyl)borate analogues are reduction resistant but have not yet yielded imido complexes. The first imido complexes of Au were prepared by treating a Au oxo complex with amines or isocyanates. Dimeric Cp*Rh dioxygen and nitrosobenzene complexes were prepared by insertion into the Rh-Rh bond of (Cp*RhCl)2. The dioxygen complex activates a C-H bond of the Cp* ligand on treatment with PMe3. Imido and oxo complexes nitrene and oxygen atom transfer product in reactions with CO. A novel electrophilic ring addition was observed with sterically protected aryl imido complexes. 15 refs.
Author: William A. Nugent
Publisher: Wiley-Interscience
ISBN:
Category : Science
Languages : en
Pages : 360
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The only comprehensive one-volume text/reference on metal-ligand multiple bonds. Stresses the unified nature of the field and includes handy new tabulations of data. The flow within each subtopic is oxygen to nitrogen to carbon. Coverage is up-to-date--virtually every subtopic leads to interesting questions for future research. Presents information otherwise scattered through hundreds of publications.
Author: Louis S. Hegedus
Publisher: University Science Books
ISBN: 9781891389047
Category : Science
Languages : en
Pages : 358
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Book Description
This second edition offers easy access to the field of organotransition metal chemistry. The book covers the basics of transition metal chemistry, giving a practical introduction to organotransition reaction mechanisms.
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Languages : en
Pages : 4
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A range of new phosphine Au(I) oxo complexes, [(LAu)[sub 3]([mu]-O)][sup +], were prepared, testing the limits of the phosphine steric and electronic properties. Their reaction with reducing agents (hydrazines, CO and RNC) give a variety of new and known gold clusters in unprecedented high yields and establish the steric and electronic relationships between the phosphine and the nuclearity of the product Au cluster. The [L[sub 2]Pt([mu]-O)][sub 2] class of dioxo complexes has been expanded to include the first anionic oxo complex, ([(dppm-H)Pt([mu]-O)][sub 2])Li[sub 2] and the first Pt imido complexes, [(L[sub 2]Pt)[sub 2]([mu]-O)([mu]-NR)] and [L[sub 2]Pt([mu]-NR)][sub 2]. The previously observed Rh imido/amido A-frame chemistry has been extended to Ir. The p-MePh-imido complex has been characterized by X-ray diffraction and clearly shows the resonance delocalization of the nitrogen lone pair into the aryl ring which is responsible for the previously observed electrophilic ring addition and oxidative ring coupling reactions.
Author: Jian-Jun Li
Publisher:
ISBN:
Category : Platinum
Languages : en
Pages : 352
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Late transition metal oxo and imido complexes are important models for catalytic reactions involving oxygen and nitrogen transfer. The subject of this dissertation is the synthesis and reactivity study of a series of platinum(II) hydroxo, oxo, amido, imido and hydrazido complexes. The platinum(II) hydroxo complex (L$\sb2$Pt($\mu$-OH)) $\rm\sb2X\sb2$ is prepared from the reaction of L$\rm\sb2PtCl\sb2$ with two equivalents of AgX. Deprotonation of the hydroxo complex (L$\rm\sb2Pt(\mu$-OH)) $\sb2\sp{2+}$ yields corresponding oxo complexes. The site of deprotonation depends on the phosphine ligands. Pt(II) $\mu$-amido complexes are synthesized from the reaction of $\mu$-hydroxo complexes (L$\rm\sb2Pt(\mu$-OH)) $\rm\sb2(BF\sb4)\sb2$ with amines H$\sb2$NR. The result of the reaction depends on the ligand L$\sb2$ of the $\mu$-hydroxo complexes as well as on the R group of the amines. Treating (L$\rm\sb2Pt(\mu$-OH)) $\rm\sb2(BF\sb4)\sb2$ with two equivalents of H$\rm\sb2NNH\sb2$ generates an unusual hydrazido complex (L$\rm\sb2Pt(\mu$-NHNH$\rm\sb2)\rbrack\sb2(BF\sb4)\sb2$ which can be deprotonated to give ((dppm-H)Pt($\mu$-NHNH$\sb2)\rbrack\sb2$.
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Category :
Languages : en
Pages : 4
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A range of new phosphine Au(I) oxo complexes, [(LAu)3([mu]-O)], were prepared, testing the limits of the phosphine steric and electronic properties. Their reaction with reducing agents (hydrazines, CO and RNC) give a variety of new and known gold clusters in unprecedented high yields and establish the steric and electronic relationships between the phosphine and the nuclearity of the product Au cluster. The [L2Pt([mu]-O)]2 class of dioxo complexes has been expanded to include the first anionic oxo complex, ([(dppm-H)Pt([mu]-O)]2)Li2 and the first Pt imido complexes, [(L2Pt)2([mu]-O)([mu]-NR)] and [L2Pt([mu]-NR)]2. The previously observed Rh imido/amido A-frame chemistry has been extended to Ir. The p-MePh-imido complex has been characterized by X-ray diffraction and clearly shows the resonance delocalization of the nitrogen lone pair into the aryl ring which is responsible for the previously observed electrophilic ring addition and oxidative ring coupling reactions.
Author: Daniel Clayton Cummins
Publisher:
ISBN: 9780355735154
Category :
Languages : en
Pages : 281
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When 9 is reacted with single oxygen atom transfer reagents the novel bridging oxo complex in the form of [TpFc,MeFe] 2(μ2-η1:η1-O) (16) is produced. 16 is only the second instance of such a FeII-O-FeII compound to have been isolated and structurally characterized. In the effort to produce additional chalcogenide compounds the complexes TpFc,MeFeOCPh3 (13) and TpFc,MeFeSCPh3 (14) were produced by salt metathesis with 3. The reaction of 14 with KH in the presence of 18-crown-6 to produce a bridging sulfide, [Tp Fc,MeFe]2(μ2-η1:η 1-S) (15). Attempts to produce imide compounds to act as isoelectronic models for terminal oxo compounds by reacting organic azides with 9 and 10 resulted in the production of tetrazene complex TpFc,MeCoN4Bn2 (17), as well as metallated azides TpFc,MeFeN3 (20) and TpFc,MeCoN3 (21).
