Group 4 Metalloporphyrin Diolato Complexes And Catalytic Application Of Metalloporphyrins And Related Transition Metal Complexes

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Group 4 Metalloporphyrin Diolato Complexes and Catalytic Application of Metalloporphyrins and Related Transition Metal Complexes

Author :
Publisher :
ISBN 13 :
Total Pages : 200 pages
Book Rating : 4.:/5 (16 download)

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Book Synopsis Group 4 Metalloporphyrin Diolato Complexes and Catalytic Application of Metalloporphyrins and Related Transition Metal Complexes by :

Download or read book Group 4 Metalloporphyrin Diolato Complexes and Catalytic Application of Metalloporphyrins and Related Transition Metal Complexes written by and published by . This book was released on 2003 with total page 200 pages. Available in PDF, EPUB and Kindle. Book excerpt: In this work, the first examples of group 4 metalloporphyrin 1,2-diolato complexes were synthesized through a number of strategies. In general, treatment of imido metalloporphyrin complexes, (TTP)M=NR, (M = Ti, Zr, Hf), with vicinal diols led to the formation of a series of diolato complexes. Alternatively, the chelating pinacolate complexes could be prepared by metathesis of (TTP)MCl2 (M = Ti, Hf) with disodium pinacolate. These complexes were found to undergo C-C cleavage reactions to produce organic carbonyl compounds. For titanium porphyrins, treatment of a titanium(II) alkyne adduct, (TTP)Ti(?2-PhC≡CPh), with aromatic aldehydes or aryl ketones resulted in reductive coupling of the carbonyl groups to produce the corresponding diolato complexes. Aliphatic aldehydes or ketones were not reactive towards (TTP)Ti(?2-PhC≡CPh). However, these carbonyl compounds could be incorporated into a diolato complex on reaction with a reactive precursor, (TTP)Ti[O(Ph)2C(Ph)2O] to provide unsymmetrical diolato complexes via cross coupling reactions. In addition, an enediolato complex (TTP)Ti(OCPhCPhO) was obtained from the reaction of (TTP)Ti(?2-PhC≡CPh) with benzoin. Titanium porphyrin diolato complexes were found to be intermediates in the (TTP)Ti=O-catalyzed cleavage reactions of vicinal diols, in which atmospheric oxygen was the oxidant. Furthermore, (TTP)Ti=O was capable of catalyzing the oxidation of benzyl alcohol and ?-hydroxy ketones to benzaldehyde and ?-diketones, respectively. Other high valent metalloporphyrin complexes also can catalyze the oxidative diol cleavage and the benzyl alcohol oxidation reactions with dioxygen. A comparison of Ti(IV) and Sn(IV) porphyrin chemistry was undertaken. While chelated diolato complexes were invariably obtained for titanium porphyrins on treatment with 1,2-diols, the reaction of vicinal diols with tin porphyrins gave a number of products, including mono-, bis-alkoxo, and chelating diolato complexes, depending on the identity of diols and the stoichiometry employed. It was also found that tin porphyrin complexes promoted the oxidative cleavage of vicinal diols and the oxidation of ?-ketols to ?-diketones with dioxygen. In extending the chemistry of metalloporphyrins and analogous complexes, a series of chiral tetraaza macrocyclic ligands and metal complexes were designed and synthesized. Examination of iron(II) complexes showed that they were efficient catalysts for the cyclopropanation of styrene by diazo reagents. Good yields and high diastereoselectivity were obtained with modest enantioselectivity. A rationalization of the stereoselectivity was presented on the basis of structural factors in a carbene intermediate.

Group Four Metalloporphyrin Diolato Complexes and Catalytic Application of Metalloporphyrins and Related Transition Metal Complexes

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Author : Guodong Du
Publisher :
ISBN 13 :
Total Pages : 384 pages
Book Rating : 4.:/5 (583 download)

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Book Synopsis Group Four Metalloporphyrin Diolato Complexes and Catalytic Application of Metalloporphyrins and Related Transition Metal Complexes by : Guodong Du

Download or read book Group Four Metalloporphyrin Diolato Complexes and Catalytic Application of Metalloporphyrins and Related Transition Metal Complexes written by Guodong Du and published by . This book was released on 2003 with total page 384 pages. Available in PDF, EPUB and Kindle. Book excerpt: In this work, the first example of group 4 metalloporphyrin 1,2-diolato complexes were synthesized through a number of strategies. In general, treatment of imido metalloporphyrin complexes, (TTP)M=NR, (M = Ti, Zr, Hf), with vicinal diols led to the formation of a series of diolato complexes. Alternatively, the chelating pinacolate complexes could be prepared by metathesis of (TTP)MCl2 (M = Ti, Hf) with disodium pinacolate. These complexes were found to undergo C-C cleavage reactions to produce organic carbonyl compounds. For titanium porphyrins, treatment of a titanium(II) alkyne adduct, (TTP)Ti([eta]2-PhC[Identical with]CPh), with aromatic aldehydes or aryl ketones resulted in reductive coupling of the carbonyl groups to produce the corresponding diolato complexes. Unreactive aliphatic aldehydes or ketones could be incorporated into a diolato complex on reaction with a reactive precursor, (TTP)Ti[O(Ph)2C(Ph)2O] to provide unsymmetrical diolato complexes. In addition, an enediolato complex (TTP)Ti(OCPhCPhO) was obtained from the reaction of (TTP)Ti([eta]2-PhC[Identical with]CPh) with benzoin. Titanium porphyrin diolato complexes were found to be intermediates in the (TTP)Ti=O-catalyzed cleavage reactions of vicinal diols, in which atmospheric oxygen was the oxidant. Furthermore, (TTP)Ti=O was capable of catalyzing the oxidation of benzyl alcohol and [alpha]-hydroxy ketones to benzaldehyde and [alpha]-diketones, respectively. Other high valent metalloporphyrin complexes also can catalyze the oxidative diol cleavage and the benzyl alcohol oxidation reactions with dioxygen. A comparison of Ti(IV) and Sn(IV) porphyrin chemistry was undertaken. While chelated diolato complexes were invariably obtained for titanium porphyrins on treatment with 1,2-diols, the reaction of vicinal diols with tin porphyrins gave a number of products, including mono-, bis-alkoxo, and chelating diolato complexes, depending on the identity of diols and the stoichimometry employed. Tin porphyrin complexes also promoted the oxidative cleavage of vicinal diols and the oxidation of [alpha]-ketols to [alpha]-diketones with dioxygen. In extending the chemistry of metalloporphyrins and analogous complexes, a series of chiral tetraaza macrocyclic ligands and metal complexes were synthesized. Examination of iron(II) complexes showed that they efficiently catalyzed the cyclopropanation of styrene by diazo reagents. Good yields and high diastereoselectivity were obtained with modest enantioselectivity. A rationalization of the stereoselectivity was presented on the basis of structural factors in a carbene intermediate.

Metalloporphyrins Catalyzed Oxidations

Author : F. Montanari
Publisher : Springer Science & Business Media
ISBN 13 : 9401722471
Total Pages : 364 pages
Book Rating : 4.4/5 (17 download)

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Book Synopsis Metalloporphyrins Catalyzed Oxidations by : F. Montanari

Download or read book Metalloporphyrins Catalyzed Oxidations written by F. Montanari and published by Springer Science & Business Media. This book was released on 2013-11-11 with total page 364 pages. Available in PDF, EPUB and Kindle. Book excerpt: Oxidative catalysis by metalloporphyrin systems occupies a prominent role in the current research in the fields of chemical and biological catalysis. Our particular interest and approach has been to collect in the same volume papers dealing with both the chemical and biological aspects of the reactivity of heme systems because of the realization that a better understanding of the complementary discipline can be extremely useful for the researchers from either field. The current progress of the research on synthetic metalloporphyrin catalysts has led to the development of several systems that are able to reproduce the heme-enzyme mediated oxygenation and oxidation reactions, at least in terms of reaction types, mechanisms and often rates. These achievements have stimulated the of creating metalloporphyrin catalysts which are both ambitious project efficient and stable enough to become competitive for large-scale industrial processes. Although this project is still far from being realized, the efforts in this direction parallel those aimed at the application of heme enzymes to chemical technologies, e. g. for the mild, selective oxidation of organics or the detoxification of pollutants. Both the two approaches will be advantageous because while the enzyme systems can achieve selectivities which are probably unattainable by synthetic catalysts, the latter can be active under experimental conditions that would readily inactivate the enzymes.

Synthesis of Group (IV) Transition Metal Complexes and Their Applications as Catalysts for Ethylene Polymerization

Author : Khalil Ahmad
Publisher :
ISBN 13 :
Total Pages : 111 pages
Book Rating : 4.:/5 (856 download)

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Book Synopsis Synthesis of Group (IV) Transition Metal Complexes and Their Applications as Catalysts for Ethylene Polymerization by : Khalil Ahmad

Download or read book Synthesis of Group (IV) Transition Metal Complexes and Their Applications as Catalysts for Ethylene Polymerization written by Khalil Ahmad and published by . This book was released on 2010 with total page 111 pages. Available in PDF, EPUB and Kindle. Book excerpt:

Dissertation Abstracts International

Author :
Publisher :
ISBN 13 :
Total Pages : 740 pages
Book Rating : 4.3/5 (91 download)

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Book Synopsis Dissertation Abstracts International by :

Download or read book Dissertation Abstracts International written by and published by . This book was released on 2004 with total page 740 pages. Available in PDF, EPUB and Kindle. Book excerpt:

Metalloporphyrins in Catalytic Oxidations

Author : Roger A. Sheldon
Publisher : CRC Press
ISBN 13 : 9780824792282
Total Pages : 412 pages
Book Rating : 4.7/5 (922 download)

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Book Synopsis Metalloporphyrins in Catalytic Oxidations by : Roger A. Sheldon

Download or read book Metalloporphyrins in Catalytic Oxidations written by Roger A. Sheldon and published by CRC Press. This book was released on 1994-06-28 with total page 412 pages. Available in PDF, EPUB and Kindle. Book excerpt: This volume provides an in-depth overview of the chemistry of metalloporphyrins as oxidation catalysts in chemical and biological systems. It discusses practical techniques for the synthesis of metalloporphyrins and introduces useful methods of immobilization to improve their synthetic utility. Detailed discussions of underlying mechanistic features are provided.

Metalloporphyrins

Author : Aleksey Kuznetsov
Publisher : Walter de Gruyter GmbH & Co KG
ISBN 13 : 3110618028
Total Pages : 123 pages
Book Rating : 4.1/5 (16 download)

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Book Synopsis Metalloporphyrins by : Aleksey Kuznetsov

Download or read book Metalloporphyrins written by Aleksey Kuznetsov and published by Walter de Gruyter GmbH & Co KG. This book was released on 2021-10-25 with total page 123 pages. Available in PDF, EPUB and Kindle. Book excerpt: Porphyrins, composed of four pyrrole subunits, are highly important compounds, which are ubiquitous in biological systems. This book reviews the factors that influence physical and chemical properties of tetrapyrrole species and explores the ways to tune geometric and electronic structures of porphyrins in order to modify their electronic, optical and magnetic characteristics.

Group 4 Metalloporphyrin Alkoxido, Amido, Hydrazido, and Imido Complexes

Author : Joseph Lyndon Thorman
Publisher :
ISBN 13 :
Total Pages : 452 pages
Book Rating : 4.:/5 (435 download)

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Book Synopsis Group 4 Metalloporphyrin Alkoxido, Amido, Hydrazido, and Imido Complexes by : Joseph Lyndon Thorman

Download or read book Group 4 Metalloporphyrin Alkoxido, Amido, Hydrazido, and Imido Complexes written by Joseph Lyndon Thorman and published by . This book was released on 1999 with total page 452 pages. Available in PDF, EPUB and Kindle. Book excerpt: These imido compounds were key starting materials for the production and investigation of a number of complexes containing M-0 bonds. The zirconium and hafnium imido complexes, (TTP)M=NAr[Sperscript Pr], couple two pinacolone molecules with concomitant loss of the amine H2NAr[Superscript Pr]. The hydrazido, (TTP)Ti=NNR2 (R = Me, Ph), and imido, (TTP)Ti=NPr, derivatives of titanium undergo novel nitrene group metathesis reactions with p-chlorobenzaldehyde and with nitrosobenzene, respectively. Additional examples of atom and group transfer involving titanium(II) metalloporphyrins have been demonstrated. Utilization of a variety of donor molecules has facilitated the estimation of the double bond strength for complexes of the type (TTP)Ti=G (G = 0, S, Se, NR). This dissertation focuses on the synthesis and reactivity of group 4 metalloporphyrin complexes containing hard [Pi]-donor ligands and on the properties of titanium(II) metalloporphyrin species.

Transition Metal Complexes of Porphyrin Analogs and Borate-based Coordination Complexes

Author : Anil Çetin
Publisher :
ISBN 13 :
Total Pages : 198 pages
Book Rating : 4.:/5 (97 download)

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Book Synopsis Transition Metal Complexes of Porphyrin Analogs and Borate-based Coordination Complexes by : Anil Çetin

Download or read book Transition Metal Complexes of Porphyrin Analogs and Borate-based Coordination Complexes written by Anil Çetin and published by . This book was released on 2007 with total page 198 pages. Available in PDF, EPUB and Kindle. Book excerpt: The synthesis of low-coordinate metal ions has been a focus of bioinorganic chemists due to their important roles in active sites in enzymes and protein. Although the isolation of these types of complexes is challenging, porphyrin analogs with one or two carbon atoms in the interior position can be good candidates for generating protected low coordinate metal sites. The metal coordination of one or two carbon substituted hemiporphyrazines, namely monocarbahemiporphyrazine and dicarbahemiporphyrazine, was investigated. These porphyrin analogs, in which one or two of the central metal binding nitrogen atoms were replaced with C-H groups, were synthesized in the early 1950s by Linstead and co-workers, but their metal binding chemistry remained unexplored. Several low coordinate metal complexes of dicarbahemiporphyrazine, namely silver, copper, manganese, iron and cobalt were synthesized. Three different cobalt complexes of monocarbahemiporphyrazine in +2 and +3 oxidation states were also synthesized. Porpholactone is another example of a ring modified porphyrin isomer. In this macrocycle one of the four pyrrollic units is oxidized to an oxazolone ring. Metal complexes of porpholactone may be novel catalysts for epoxidation of alkenes. The synthesis and X-ray crystal structure of first manganese complex of the porpholactone 5,10,15,20-tetraphenylporpholactone are reported. The catalytic activity of the complex by using a variety of substrates was explored and it was compared with that of manganese tetraphenylporphyrin. Metal complexes of a sulfur containing borate-based chelating ligand, tris(imazolyl)borate, HB(mt)3− were examined. Three different modes of interaction were observed with divalent closed d shell metal metal cations: Ca(II), Ba(II) and Hg(II). This study exhibits the diversity of binding not typically observed in the scorpionate family. With group II and group XII metals, the HB(mt)3− ligand can act as a non-coordinating anion, can engage in B-H agostic bonding, and can form metal cluster compounds. Molecular organization of guest molecules within nanometer-sized structures is a big challenge in terms of controlling the physical properties and chemical reactivities. In our group, we are investigating borate-based coordination polymer, lead tetrakis(imidazolyl)borate, to organize and sequester anionic guests. A variety of anionic guests were organized within the layers lead(II) borate scaffolds. The possibility of topochemical polymerization of these pre-organized anionic monomers in the crystalline state was explored.

Metalloporphyrins Or Vanadium (oxo) Complexes and Their Applications to Bond Activation Chemistry

Author : Rui Zhang
Publisher :
ISBN 13 :
Total Pages : 235 pages
Book Rating : 4.:/5 (129 download)

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Book Synopsis Metalloporphyrins Or Vanadium (oxo) Complexes and Their Applications to Bond Activation Chemistry by : Rui Zhang

Download or read book Metalloporphyrins Or Vanadium (oxo) Complexes and Their Applications to Bond Activation Chemistry written by Rui Zhang and published by . This book was released on 2021 with total page 235 pages. Available in PDF, EPUB and Kindle. Book excerpt: Recent developments in new molecular designs, scaling relationships, and theoretical modeling of mechanisms have rapidly advanced the utility of metalloporphyrins as electrocatalysts in the activation of small molecules, in particular O2 and CO2. The development and improvement of electrocatalysts for the 4H+ /4e− reduction of O2 to H2O, and for the CO2 reduction reaction (CO2RR) to provide a route to turn a greenhouse gas into value-added products, are ongoing challenges. The addition of ancillary groups (e.g., hydrogen bonding, Brønsted acid/base) near the active site of metal-containing catalysts is an effective way to improve the selectivity and kinetics of the oxygen reduction reaction (ORR) and CO2RR. In this regard, iron porphyrins are among the most researched ORR/CO2RR catalysts. Closely related cobalt porphyrin catalysts can function closer to the O2/H2O thermodynamic potential and can reduce CO2 at a lower overpotentials, but they tend to be less selective and follow a different mechanism than iron porphyrins. Here, I explore strategies to extend the ideas about ancillary groups that have been developed for iron porphyrin ORR/CO2RR electrocatalysts to improve the performance of the corresponding cobalt complexes. I describe a series of porphyrin electrocatalysts for ORR/CO2RR that are modified versions of Co(5,10,15,20-tetraphenylporphyrin), where the 2-position of one of the phenyl groups contains -NH2, -N(CH3)2, and -N(CH3)3+. In Chapter 2, the presence of a cationic ancillary group gives rise to a catalyst that is selective for the conversion of O2 to H2O across a wide pH range. Electrostatic groups for cobalt porphyrins enhance the performance of 4e- reduction of O2 to H2O, while protic ancillary groups are important in the performance of iron porphyrin ORR catalysts. In Chapter 3 and 4, homogeneous and heterogeneous CO2RR are studied, respectively. For cobalt porphyrins, protic hydroxyphenyl ancillary groups aid in production of CO, while electrostatic stabilizers of CO2-bound intermediates seem to favor other CO2 reduction products. These studies show that the second sphere interactions for ancillary groups of metalloporphyrins must be carefully designed for different metals and different reactions. In addition, the photochemical activation of carbon-hydrogen bonds by vanadium-dioxo (VV(O)(O)) and vanadium-oxo-peroxo (VV(O)(O2)) diimine complexes is described in Chapter 5. The involvement of electronically excited V complexes as radical reaction initiators is described.

Transition Metal Complexes with P,N-ligands and Silylenes

Author : Eva Neumann
Publisher :
ISBN 13 : 9783865378019
Total Pages : 239 pages
Book Rating : 4.3/5 (78 download)

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Book Synopsis Transition Metal Complexes with P,N-ligands and Silylenes by : Eva Neumann

Download or read book Transition Metal Complexes with P,N-ligands and Silylenes written by Eva Neumann and published by . This book was released on 2006 with total page 239 pages. Available in PDF, EPUB and Kindle. Book excerpt:

Directory of Graduate Research

Author : American Chemical Society. Committee on Professional Training
Publisher :
ISBN 13 :
Total Pages : 1932 pages
Book Rating : 4.:/5 (318 download)

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Book Synopsis Directory of Graduate Research by : American Chemical Society. Committee on Professional Training

Download or read book Directory of Graduate Research written by American Chemical Society. Committee on Professional Training and published by . This book was released on 2005 with total page 1932 pages. Available in PDF, EPUB and Kindle. Book excerpt: Faculties, publications and doctoral theses in departments or divisions of chemistry, chemical engineering, biochemistry and pharmaceutical and/or medicinal chemistry at universities in the United States and Canada.

Commencement

Author : Iowa State University
Publisher :
ISBN 13 :
Total Pages : 562 pages
Book Rating : 4.:/5 (318 download)

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Book Synopsis Commencement by : Iowa State University

Download or read book Commencement written by Iowa State University and published by . This book was released on 2001 with total page 562 pages. Available in PDF, EPUB and Kindle. Book excerpt:

Synthesis and Characterization of Metal Metal Multiply Bonded Complexes and Catalytic Applications of Solvent Stabilized Transition Metal Complexes for Polymerization of Olefins

Download Synthesis and Characterization of Metal Metal Multiply Bonded Complexes and Catalytic Applications of Solvent Stabilized Transition Metal Complexes for Polymerization of Olefins PDF Online Free

Author : Guofang Zhang
Publisher :
ISBN 13 :
Total Pages : 136 pages
Book Rating : 4.:/5 (216 download)

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Book Synopsis Synthesis and Characterization of Metal Metal Multiply Bonded Complexes and Catalytic Applications of Solvent Stabilized Transition Metal Complexes for Polymerization of Olefins by : Guofang Zhang

Download or read book Synthesis and Characterization of Metal Metal Multiply Bonded Complexes and Catalytic Applications of Solvent Stabilized Transition Metal Complexes for Polymerization of Olefins written by Guofang Zhang and published by . This book was released on 2001 with total page 136 pages. Available in PDF, EPUB and Kindle. Book excerpt:

Synthesis of New Transition Metal Complexes and Applications for the Catalytic Ethylene Oligomerization and /or Polymerization

Author : Suyun Jie
Publisher :
ISBN 13 :
Total Pages : 286 pages
Book Rating : 4.:/5 (866 download)

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Book Synopsis Synthesis of New Transition Metal Complexes and Applications for the Catalytic Ethylene Oligomerization and /or Polymerization by : Suyun Jie

Download or read book Synthesis of New Transition Metal Complexes and Applications for the Catalytic Ethylene Oligomerization and /or Polymerization written by Suyun Jie and published by . This book was released on 2008 with total page 286 pages. Available in PDF, EPUB and Kindle. Book excerpt: Polyolefins represent about half the market of the synthesized polymeric materials. The catalytic oligomerization of ethylene is currently the primary source of linear [alpha]-olefins which are extensively used for the preparation of synthetic lubricants, detergent intermediates, surfactants, plasticizers and as comonomers to synthesize linear low-density polyethylene (LLDPE). This work deals with the synthesis of 2-imino-1,10-phenanthroline and 2-imino-9-phenyl-1,10-phenanthroline tridentate ligand and of their iron, cobalt and nickel complexes of which some are very active in the catalytic ethylene oligomerization. Stereoelectronic parameters influencing the catalytic properties have been examined in detail. Furthermore, mono- and dinuclear cobalt complexes with phosphino- and phosphinito-oxazoline ligands have been prepared in the course of this thesis. They have shown moderate catalytic activity in the presence of MAO or AlEtCl2 as cocatalyst.

Synthesis and Catalytic Applications of Transition Metal Complexes of Di-N-heterocyclic Carbenes Incorporating an Amine Functionality

Download Synthesis and Catalytic Applications of Transition Metal Complexes of Di-N-heterocyclic Carbenes Incorporating an Amine Functionality PDF Online Free

Author :
Publisher :
ISBN 13 :
Total Pages : 304 pages
Book Rating : 4.:/5 (931 download)

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Book Synopsis Synthesis and Catalytic Applications of Transition Metal Complexes of Di-N-heterocyclic Carbenes Incorporating an Amine Functionality by :

Download or read book Synthesis and Catalytic Applications of Transition Metal Complexes of Di-N-heterocyclic Carbenes Incorporating an Amine Functionality written by and published by . This book was released on 2005 with total page 304 pages. Available in PDF, EPUB and Kindle. Book excerpt:

Late Transition-metal Complexes Supported by Pincer Ligands

Author : Wilson D. Bailey
Publisher :
ISBN 13 :
Total Pages : 181 pages
Book Rating : 4.:/5 (989 download)

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Book Synopsis Late Transition-metal Complexes Supported by Pincer Ligands by : Wilson D. Bailey

Download or read book Late Transition-metal Complexes Supported by Pincer Ligands written by Wilson D. Bailey and published by . This book was released on 2016 with total page 181 pages. Available in PDF, EPUB and Kindle. Book excerpt: Late transition-metal pincer complexes of primarily palladium(II) and platinum(II) have been investigated for their application as catalysts in partial oxidation reactions. The epoxidation of higher olefins using molecular oxygen as the oxidant has been targeted, and the individual reaction steps needed to accomplish this overall transformation are described herein, including: (1) hydrogenolysis of a metal hydroxide (M-OH) species to yield a metal hydride (M-H), (2) insertion of O2 into the M-H bond to form a metal hydroperoxide (M-OOH), and (3) O-atom transfer from the M-OOH to epoxides, yielding a M-OH and completing the catalytic cycle. Previous results from our group on these individual transformations using (tBuPCP)Pd and (tBuPCO)Pd fragments are also reviewed. The requirements for O2 insertion into PdII and PtII hydrides are discussed. An array of cationic, neutral, and anionic Pd-H and Pt-H complexes supported by a tBuPNP backbone were synthesized and evaluated for O2 insertion (tBuPNP = 2,6-bis-(di-tbutylphosphinomethyl)pyridine). Metal-ligand cooperation was observed in the activation of H2 to form neutral hydride complexes. The effect of ligand protonation/deprotonation on the trans influence experienced by the hydride ligand was investigated. No reaction with O2 was observed with the cationic hydrides, while the neutral and anionic forms reacted with O2 at the tBuPNP backbone. The synthesis and characterization of mono- and dinuclear Pd-OH complexes supported by a PCNR pincer ligand (PCNR = (1-(3-((di-tert-butylphosphino)methyl)phenyl)-1H-5-R-pyrazole), R = H, Me) is presented. When R = H, ligand pyrazole "rollover" C-H activation was observed, forming a mixed ligand (PCNH)Pd(μ-OH)Pd(PCC) dinuclear structure. This "rollover" was investigated using DFT computations. The mono- and dinuclear hydroxide species were evaluated for hydrogenolysis. The dinuclear compounds {[(PCNR)Pd]2(μ-OH)}[OTf] reacted under an H2 atmosphere to yield the corresponding dinuclear hydrides {[(PCNR)Pd]2(μ-H)}[OTf]. A mechanistic study on the hydrogenolysis of the μ-bridged hydroxide {[(PCNMe)Pd]2(μ-OH)}[OTf] revealed first order kinetics in both [Pd] and [H2]. Terminal hydrides were not detected, and reduction of the mononuclear hydroxide complexes (PCNR)Pd-OH to Pd0 was observed under H2. The reduction was proposed to proceed through displacement of the pyrazole arm, and was examined by DFT computations. Lastly, a new strategy to promote O-atom transfer from M-OOH to epoxides, the final step in the targeted catalytic cycle, is proposed. Preliminary studies on NNNPyz, NNNEt, and NNMe ligated PdII and PtII are discussed (NNNPyz = 2,6-bis(5-tbutyl-1H-pyrazol-3-yl)pyridine; NNNEt = 2-(5-tbutyl-1H-pyrazol-3-yl)-6-(diethylaminomethyl)pyridine; NNMe = 2-(5-tBu-1H-pyrazol-3-yl)-6-methylpyridine). The NNNPyz ligand, containing two acidic sites in proximity to the fourth site in the square plane, was found to protonate M-O2 complexes, chelate to the metal center and oxidize phosphine substrates. Similar reactivity was observed with NNNEt and NNMe, however hemilability of these ligands resulted in undesired coordination modes.