자료유형  

 학위논문

Control Number  

0015492693

International Standard Book Number  

9781392335406

Dewey Decimal Classification Number  

547

Main Entry-Personal Name  

McCarthy, Sean M.

Publication, Distribution, etc. (Imprint  

[Sl] : The Pennsylvania State University, 2017

Publication, Distribution, etc. (Imprint  

Ann Arbor : ProQuest Dissertations & Theses, 2017

Physical Description  

373 p

General Note  

Source: Dissertations Abstracts International, Volume: 81-01, Section: B.

General Note  

Publisher info.: Dissertation/Thesis.

General Note  

Advisor: Funk, Raymond L.

Dissertation Note  

Thesis (Ph.D.)--The Pennsylvania State University, 2017.

Summary, Etc.  

요약The activations of O-H and N-H bonds via oxidative addition are of significant importance as initiatory steps toward catalytic alcohol and amine functionalization. Such a transformation is classically considered the purview of transition metal based catalysts, which have appropriate orbital symmetry and energies for effecting bond cleavage. However, catalysis using main group compounds has recently become an area of growing interest, due to concerns about the cost and negative environmental impact of precious metal use. In this vein, we have investigated the use of phosphorus-based catalysts as transition metal surrogates for bond activation. By enforcing bond angle strain in phosphorus (III) species, one can manipulate the frontier orbitals associated with the phosphorus center to access previously unknown reactive modes. Using this strategy, we have developed two platforms for the largely unprecedented intermolecular activations of O-H and N-H bonds at phosphorus and investigated their mechanisms in depth. Chapter 2 discusses the scope and thermodynamics of an N-H oxidative addition to a planar, C2v symmetric phosphabicycle to form stable amidohydridophosphorane products. Chapter 3 details a comprehensive study of the mechanism of this reaction, using a combination kinetic and computational studies to reveal a highly unusual entropy controlled electrophilic pathway. In Chapter 4, the design, synthesis, and characterization of a complementary bent Cs symmetric phosphorous triamide is described. Chapter 5 discusses the scope and mechanism of reversible O-H and N-H oxidative additions to this species, along with detailed structural characterizations of the P(V) adducts obtained as products. Finally, Chapter 6 describes initial efforts toward applying this unique reactivity towards synthetically useful methods. Taken together, this research provides significant insight into the relationship between structure and reactivity in trivalent phosphorus compounds and represents an initial step toward the development of phosphorus-based mimics for transition metal catalysts.

Subject Added Entry-Topical Term  

Chemistry

Subject Added Entry-Topical Term  

Inorganic chemistry

Subject Added Entry-Topical Term  

Organic chemistry

Added Entry-Corporate Name  

The Pennsylvania State University Chemistry

Host Item Entry  

Dissertations Abstracts International. 81-01B.

Host Item Entry  

Dissertation Abstract International

Electronic Location and Access  

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Control Number  

joongbu:565039