Author: Leo Dale Brown
Publisher:
ISBN:
Category :
Languages : en
Pages : 332
Book Description
Cobalt Cyanide and Isocyanide Complexes, Their Preparation, Structure, and Bonding
Author: Leo Dale Brown
Publisher:
ISBN:
Category :
Languages : en
Pages : 332
Book Description
Publisher:
ISBN:
Category :
Languages : en
Pages : 332
Book Description
Low-Valent Iron and Cobalt Isocyanide Complexes
Author: Charles Cameron Mokhtarzadeh
Publisher:
ISBN:
Category :
Languages : en
Pages : 434
Book Description
This dissertation describes the targeted attempts at the generation of transition metal species that function as precise electronic structure mimics to the well known spin triplet (S =1) metal carbonyls fragments Fe(CO)4 and CpCo(CO). These unsaturated fragments have been shown to display a wide range reactivity, and competency towards important reaction chemistry such as alkane and N2 binding, and E-H bond activation due to a unique interplay of a strong ligand field, formal dn count, and orbital symmetry, rendering these fragments primed for bond activation. Accordingly, ligand architectures that can accurately mimic the ligand field provided by CO to kinetically stabilize these fragments could provide new inroads to novel small molecule activation pathways. To this end, sterically encumbering m-terphenyl isocyanides serve as isolobal ligand surrogates for carbon monoxide (CO). Additionally isocyanides have the added benefit of providing kinetic stabilization by virtue of readily tunable isocyano-R (CN-R) group. The first section of this dissertation describes the synthesis and protonation of an encumbered tetra-isocyanide iron dianion, Na2[Fe(CNArMes2)4] (ArMes2 = 2,6-(2,4,6 --Me3C6H2)2C6H3), which serves as a platform for targeting species of the formulation Fe(CNArMes2)4. It is shown that the reactivity of the electronically unsaturated Fe(CNR)4 fragment upon protonation of Na2[Fe(CNArMes2)4] and subsequent alkylation of Na[HFe(CNArMes2)4], yields the dinitrogen stabilized species Fe(N2)(CNArMes2)4. Fe(N2)(CNArMes2)4 is shown to readily undergo intramolecular C-H activation of the ligand scaffold upon liberation N2 under ambient conditions purportedly through and insipient [Fe(CNArMes2)4] fragment. Further more, ability of Na2[Fe(CNArMes2)4] to facilitate the reductive disproportionation of CO2, in addition to CO2 capture with electrophilic silyl sources is presented culminating in a rare class of low valent Fe-aminocarbyne complexes. The second vignette of this dissertation focuses on the generation of species that mimic the formulation CpCo(L). It is shown that with less encumbering m-terphenyl isocyanides that aggregation akin to the unsaturated carbonyl congeners is realized. Use of encumbering m-terphenyl isocyanides provides access to the three memebered electron transfer series [([mu]2-CNArMes2)2[CpCo]2]n (n = 0,-1, -2). Notably, this series is the first of its kind to span all three ostensible electronic states (e.g. d8-d8, d8-d9, and d9-d9), previously unavailable with other [pi]-acidic ligand frameworks. Additionally this allows for a systematic reassessment of the metal-metal bonding within this class of dimeric species. Evidence is put forth in favor of no M-M bonding interactions occur within these systems and the integrity of the dimeric framework is in fact mitigated through a unique interplay of the metal d-manifold and the isocyanide [pi]*-system. Modulation of the steric profile of the m-terphenyl isocyanide and the Cp unit to Cp* so as to increase the steric pressure provides access to the first reported mono-nuclear Cp*Co(N2)L fragments. It is shown that these species function as viable sources of Cp*Co(CNR) for a number of bond activation processes including Si-H, H-H, and P-P bond scission. Moreover, the reactivity of these species culminates with the isolation of the second example of a structurally authenticated transition metal nitrous oxide (N2O) adduct, which exhibits an unprecedented [eta]2-(N,N) coordination mode to Co. Finally, the reduction of the encumbered Cp*Co(CNArTripp2) (CNArTripp2 2,6-(2,4,6-(i-Pr)3C6H3)2C6H3) fragment provide access to the unique dianion K2[Cp*Co≡CNArTripp2]. It is shown that the dianion K2[Cp*Co≡CNArTripp2] exhibits 3-fold bonding between Co and the isocyanide -Ciso through an extreme case of M-->(CN) [pi]*-back donation and gives rise to the first example of a Co-carbyne complex. The reactivity and electronic structure are presented for K2[Cp*Co≡CNArTripp2] and it is concluded that this reactive dianion behaves as a potent metal based nucleophile and source of [Cp*Co(CNR)]2- for a number of bond activation process.
Publisher:
ISBN:
Category :
Languages : en
Pages : 434
Book Description
This dissertation describes the targeted attempts at the generation of transition metal species that function as precise electronic structure mimics to the well known spin triplet (S =1) metal carbonyls fragments Fe(CO)4 and CpCo(CO). These unsaturated fragments have been shown to display a wide range reactivity, and competency towards important reaction chemistry such as alkane and N2 binding, and E-H bond activation due to a unique interplay of a strong ligand field, formal dn count, and orbital symmetry, rendering these fragments primed for bond activation. Accordingly, ligand architectures that can accurately mimic the ligand field provided by CO to kinetically stabilize these fragments could provide new inroads to novel small molecule activation pathways. To this end, sterically encumbering m-terphenyl isocyanides serve as isolobal ligand surrogates for carbon monoxide (CO). Additionally isocyanides have the added benefit of providing kinetic stabilization by virtue of readily tunable isocyano-R (CN-R) group. The first section of this dissertation describes the synthesis and protonation of an encumbered tetra-isocyanide iron dianion, Na2[Fe(CNArMes2)4] (ArMes2 = 2,6-(2,4,6 --Me3C6H2)2C6H3), which serves as a platform for targeting species of the formulation Fe(CNArMes2)4. It is shown that the reactivity of the electronically unsaturated Fe(CNR)4 fragment upon protonation of Na2[Fe(CNArMes2)4] and subsequent alkylation of Na[HFe(CNArMes2)4], yields the dinitrogen stabilized species Fe(N2)(CNArMes2)4. Fe(N2)(CNArMes2)4 is shown to readily undergo intramolecular C-H activation of the ligand scaffold upon liberation N2 under ambient conditions purportedly through and insipient [Fe(CNArMes2)4] fragment. Further more, ability of Na2[Fe(CNArMes2)4] to facilitate the reductive disproportionation of CO2, in addition to CO2 capture with electrophilic silyl sources is presented culminating in a rare class of low valent Fe-aminocarbyne complexes. The second vignette of this dissertation focuses on the generation of species that mimic the formulation CpCo(L). It is shown that with less encumbering m-terphenyl isocyanides that aggregation akin to the unsaturated carbonyl congeners is realized. Use of encumbering m-terphenyl isocyanides provides access to the three memebered electron transfer series [([mu]2-CNArMes2)2[CpCo]2]n (n = 0,-1, -2). Notably, this series is the first of its kind to span all three ostensible electronic states (e.g. d8-d8, d8-d9, and d9-d9), previously unavailable with other [pi]-acidic ligand frameworks. Additionally this allows for a systematic reassessment of the metal-metal bonding within this class of dimeric species. Evidence is put forth in favor of no M-M bonding interactions occur within these systems and the integrity of the dimeric framework is in fact mitigated through a unique interplay of the metal d-manifold and the isocyanide [pi]*-system. Modulation of the steric profile of the m-terphenyl isocyanide and the Cp unit to Cp* so as to increase the steric pressure provides access to the first reported mono-nuclear Cp*Co(N2)L fragments. It is shown that these species function as viable sources of Cp*Co(CNR) for a number of bond activation processes including Si-H, H-H, and P-P bond scission. Moreover, the reactivity of these species culminates with the isolation of the second example of a structurally authenticated transition metal nitrous oxide (N2O) adduct, which exhibits an unprecedented [eta]2-(N,N) coordination mode to Co. Finally, the reduction of the encumbered Cp*Co(CNArTripp2) (CNArTripp2 2,6-(2,4,6-(i-Pr)3C6H3)2C6H3) fragment provide access to the unique dianion K2[Cp*Co≡CNArTripp2]. It is shown that the dianion K2[Cp*Co≡CNArTripp2] exhibits 3-fold bonding between Co and the isocyanide -Ciso through an extreme case of M-->(CN) [pi]*-back donation and gives rise to the first example of a Co-carbyne complex. The reactivity and electronic structure are presented for K2[Cp*Co≡CNArTripp2] and it is concluded that this reactive dianion behaves as a potent metal based nucleophile and source of [Cp*Co(CNR)]2- for a number of bond activation process.
The Vitamin D Cure
Author: Lamberto Malatesta
Publisher: Wiley-Interscience
ISBN:
Category : Health & Fitness
Languages : en
Pages : 216
Book Description
Groundbreaking new research has traced the source of a wide array of to a single common factor—vitamin D deficiency. Leading rheumatologist and researcher Dr. James Dowd reveals the causes of vitamin D deficiency and offers a simple, easy-to-follow five-step program that can eliminate or alleviate a host of seemingly incurable conditions, such as arthritis, in as little as six weeks. Better yet, by staying on the program, you can enjoy robust health and improved fitness for the rest of your life.
Publisher: Wiley-Interscience
ISBN:
Category : Health & Fitness
Languages : en
Pages : 216
Book Description
Groundbreaking new research has traced the source of a wide array of to a single common factor—vitamin D deficiency. Leading rheumatologist and researcher Dr. James Dowd reveals the causes of vitamin D deficiency and offers a simple, easy-to-follow five-step program that can eliminate or alleviate a host of seemingly incurable conditions, such as arthritis, in as little as six weeks. Better yet, by staying on the program, you can enjoy robust health and improved fitness for the rest of your life.
Isocyanide Complexes of Cobalt
Author: Omar Ali Sabbak
Publisher:
ISBN:
Category :
Languages : en
Pages : 100
Book Description
Publisher:
ISBN:
Category :
Languages : en
Pages : 100
Book Description
Mechnaistic Study of Isocyanide Insertion Reaction Into the Platinum-carbon Sigma Bond and Molecular Structure of Two Platinum Isocyanide Complexes
Author: Kit Ming Mak
Publisher:
ISBN:
Category :
Languages : en
Pages : 366
Book Description
Publisher:
ISBN:
Category :
Languages : en
Pages : 366
Book Description
Chemical and Structural Properties of Cyanide and Isocyanide Complexes of Molybdenum
Author: Miroslav Novotny
Publisher:
ISBN:
Category : Cyanides
Languages : en
Pages : 252
Book Description
Publisher:
ISBN:
Category : Cyanides
Languages : en
Pages : 252
Book Description
Comprehensive Dissertation Index
Author:
Publisher:
ISBN:
Category : Dissertations, Academic
Languages : en
Pages : 712
Book Description
Publisher:
ISBN:
Category : Dissertations, Academic
Languages : en
Pages : 712
Book Description
Comprehensive Organometallic Chemistry
Author: Geoffrey Wilkinson
Publisher:
ISBN:
Category : Organometallic chemistry
Languages : en
Pages : 650
Book Description
Publisher:
ISBN:
Category : Organometallic chemistry
Languages : en
Pages : 650
Book Description
Synthesis, Structure and Reactivity of Cobalt and Copper Complexes with Metal-ligand Multiple Bonds Supported by Beta-diketiminate Ligands
Author: Xuliang Dai
Publisher:
ISBN:
Category : Catalysts
Languages : en
Pages : 512
Book Description
Publisher:
ISBN:
Category : Catalysts
Languages : en
Pages : 512
Book Description
Comprehensive Dissertation Index: Chemistry, E-O
Author: University Microfilms International
Publisher:
ISBN:
Category : Dissertations, Academic
Languages : en
Pages : 858
Book Description
Publisher:
ISBN:
Category : Dissertations, Academic
Languages : en
Pages : 858
Book Description