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Dissertation Information for Jeffrey T. Rhule

NAME:
- Jeffrey T. Rhule

DEGREE:
- Ph.D.

DISCIPLINE:
- Chemistry

SCHOOL:
- Emory University (USA) (2001)

ADVISORS:
- Craig L. Hill

COMMITTEE MEMBERS:
- Fred M. Menger
- Luigi G. Marzilli

MPACT Status: Fully Complete

Title: New polyoxometalate heterogeneous and homogeneous catalytic systems for oxidation of thioethers and acetaldehyde under ambient conditions

Abstract: "The work presented in this dissertation focuses on the synthesis, characterization and catalytic chemistry of transition metal salt polyoxometalates. Ag 5 PV 2 Mo 10 O 40 , [CO(CH 3 CN) 4 (H 2 O) 2 ][{CH 3 C(CH 2 O) 3 } 2 V 6 O 13 ], and [Na 2 {CH 3 C(CH 2 O) 3 } 2 V 6 O 13 ]·7H 2 O were all synthesized and evaluated as catalysts for the oxidation of thioether chemical warfare agent simulants (Ag 5 PV 2 Mo 10 O 40 ) and acetaldehyde ([Co(CH 3 CN) 4 (H 2 O) 2 ]-[{CH 3 C(CH 2 O) 3 } 2 V 6 O 13 ], and [Na 2 {CH 3 C(CH 2 O) 3 } 2 V 6 O 13 ]·7H 2 O). Oxidation of chemical warfare agents is important for the battlefield protection of troops and equipment as well as ""environmentally friendly"" methods for the destruction of large stockpiles. Acetaldehyde and other aldehydes are indoor pollutants originating from the prevalent use of synthetic fabrics and construction materials. These compounds have recently been associated with toxicological effects in humans.

Chapter 1 provides a very brief and general overview of polyoxometalates (POMs). Included is a discussion of the basic structural chemistry of POMs and fields of application where POMs are utilized. Also included is a discussion of POMs as oxidation catalysts in thermal and radical chain initiated oxidations. Activation of molecular oxygen by POMs is also addressed.

Chapter 2 presents the synthesis, characterization and catalysis of Ag 5 PV 2 Mo 10 O 40 . Under heterogeneous conditions, Ag 5 PV 2 Mo 10 O 40 , was found to be an effective catalyst for the selective oxidation of 2-chloroethyl ethyl sulfide (CEES, an analog for mustard (HD)) under ambient conditions (room temperature and air). The heterogeneous nature of the system prevented meaningful rate law determination. Absolute structural determination of Ag 5 PV 2 Mo 10 O 40 was accomplished by X-ray crystallography. When crystallized from MeCN and Et 2 O Ag 5 PV 2 Mo 10 O 40 is a dimer of 2 PV 2 Mo 10 O 40 5- molecules linked by 2 bridging Ag(I) atoms.

Chapters 3 and 4 examine the synthesis and characterization of [Co(CH 3 CN) 4 (H 2 O) 2 ][(CH 3 C(CH 2 O) 3 } 2 V 6 O 13 ] and [Na 2 {CH 3 C(CH 2 O) 3 } 2 V 6 O 13 ]·7H 2 O. Aside from standard methods of characterization (e.g. NMR, IR, elemental analysis, etc.), the structure of both complexes was determined by X-ray crystallography. The application of both catalysts for the heterogeneous oxidation of acetaldehyde at room temperature is presented along with rudimentary mechanistic information. A more rigorous and detailed examination of the rate law and mechanism for homogeneous acetaldehyde autoxidation under ambient conditions catalyzed by [Co(CH 3 CN) 4 (H 2 O) 2 ][(CH 3 C(CH 2 O) 3 } 2 V 6 O 13 ] is presented in Chapter 4."

MPACT Scores for Jeffrey T. Rhule

A = 0
C = 0
A+C = 0
T = 0
G = 0
W = 0
TD = 0
TA = 0
calculated 2008-04-07 08:09:22

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