Graduated Students and Postdoctorals 1' Dr' Miguel MunozHernandez 19982000, Quernavaca Univ' 2' Tim

1
Group 13 Acknowledgements
Graduated Students and Postdoctorals1. Dr.
Miguel Munoz-Hernandez (1998-2000, Quernavaca
Univ.)2. Tim Keizer (PhD, 2002, PD, Los Alamos,
Nalco, IL)3. Yuzhong Wang (PhD, 2003, PD, UGA,
Robinson, Adjunct Prof.)4. Dr. Melanie Harvey
(2001-2003, College of Mary, KS)5. Brandon
Conley (BS 2003, GS, MIT)6. Mary Proffitt (BS,
2003, UK-Med. School) 7. Mario Sanchez (2003,
Exchange Student, H. Hopfl)8. Lauren DePue (BS,
2004, GS,UT-Austin, Jones)9. Amithaba Mitra
(PhD, 2006, PD-UW-Madison, West)10. Jeff Struss
(BS, 2006, GS, EKU-Otieno) Current StudentsGS
Kamruz Zaman (2007), Niladri Gupta (2007), Lisa
Blue (2008),Eduardo Santillan (2008), Mustafa
Tabar, Partha Jana UG Kyle Sloan, Railey
White, David Clem, Jared Daughtery, Laura
Fletcher, Crystal Holcomb
Current FundingNSF-EPSCoR, Environmental
Training Laboratory (2005 - 2008)Merloc, LLC,
Lexington, KY (2005 - present), REB Associates
(pending), Quansor Inc. (pending)
2
Phosphate Ester Cleavage Cationic Group 13
Chelates
Atwood and Harvey, Chem. Rev. 101 (2001) 37
3
Exploration of Chelated Dinuclear Dications
Keizer, Atwood, Unpublished Results
4
Discovery Partial Dealkylation
Salpen(tBu)(BCl2)2
B-O 1.42 Å B-N 1.55 Å B-Cl 1.85 Å
3
2 (MeO)3PO
2 MeCl LB2(OPO(OMe)22 2Cl- 32
conversion after 24 h Best is sapten(tBu)(BCl2)2
with 62
5
Cationic Chelates From Bromides
6
Formation of Salen(BBr2)2
LB(OMe)22 2/3 BBr3 L(BBr2)2 B(OMe)3
(Deng, Jacobsen, J. Org. Chem. 57 (1992) 4320)
Salhen(tBu)(BBr2)2
B-O 1.42 Å B-N 1.52 Å B-Br 2.04 Å
Keizer, De Pue, Parkin, Atwood, J. Am. Chem. Soc.
124 (2002) 1864. Keizer, De Pue, Parkin, Atwood,
J. Organomet. Chem. 666 (2003) 103. Chlorides
Keizer, De Pue, Parkin, Atwood, Can. J. Chem. 80
(2002) 1463.
7
Phosphate Cleavage with Salen(BBr2)2
Cleavage of all P-O-C linkages. Up to 99
conversion in 30 minutes. Phosphate-coordinated
cationic intermediates.
Keizer, DePue, Parkin, Atwood, J. Am. Chem. Soc.
124 (2002) 1864-1865
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Catalytic Phosphate Dealkylation
Patent Catalytic Cleavage of Phosphate Ester
Bonds with Boron Chelates US Patent 7,166,591
(Jan. 23, 2007)
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Mononuclear Boron Halides
2.2 Å
Mitra, Struss, Patel, Parkin, Atwood Inorg.
Chem. 45 (2006) 9213
10
Steps in Complete Dealkylation
B-O-P, 132 B-O1, 1.43 Å B-O2, 1.46 Å B-O3, 1.48
Å
Mitra, Struss, Patel, Parkin, Atwood Inorg.
Chem. 45 (2006) 9213
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Dealkylation with SalenB(p-tol)Br2
2 (RO)3PO
3
6 RBr Chelate Product
Complete Dealkylation
Keizer, DePue, Parkin, Atwood, J. Organomet.
Chem. 666 (2003) 103
12
Single-Site Dealkylation?
Five-Coordinate Intermediate
Cation Formation
Y. Yamamoto J. Am. Chem. Soc. 127 (2005) 4354
Intermolecular
13
Hydrolysis Products Readily Form
B-O-B 117.2
B-O-B 135
Sanchez, Keizer, Parkin, Hopfl, Atwood, J.
Organomet. Chem. 654 (2002) 36. Sanchez, Hopfl,
Ochoa, Farfan, Santillan, Rojas, Inorg. Chem. 40
(2001) 6405. Siloxide Derivatives Keizer, De
Pue, Parkin, Atwood, J. Cluster Sci. 13 (2002)
609.
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Goals of current research
Amithaba Mitra, Ph.D. Spring 2006
15
Mitra in Madison with Bob West
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Salen Aluminum Bromides
Yield 55-74 , 27Al NMR ? 32-38 ppm
Mitra, DePue, Parkin, Atwood, J. Am. Chem. Soc.
128 (2006) 1147-1153. Cleavage of Phosphate
Ester Bonds by Use of Novel Group 13 Chelate
Compounds U.S. Patent 7,105,703 (Sept. 12,
2004).
17
Structure of Salben(tBu)AlBr
Trigonal Bipyramidal
Salen, Salpen, Salben, SalophenAl-Br distance
2.35-2.36 Å
Mitra, DePue, Parkin, Atwood, J. Am. Chem. Soc.
128 (2006) 1147.
18
Structure of Salophen(tBu)AlBr
Square-Pyramidal
J. Am. Chem. Soc. 128 (2006) 1147.
19
Dealkylation of Organophosphates
3 LAlBr (RO)3PO (LAl)3PO
3 R-Br
TMP, Trimethyl phosphate TEP, Triethyl
phosphate TBP, Tri-butyl phosphate
This demonstrates removal of three alkyl
groups - The nerve gas application only requires
the removal of one, which takes place
instantaneously in these systems.
Mitra, DePue, Parkin, Atwood, J. Am. Chem. Soc.
128 (2006) 1147
20
Cation Formation From SalenAlBr
salpen(tBu)Al(Ph3PO)2Br)
salophen(tBu)Al(Ph3PO)2Br
Axial Al-O, 1.92-1.97 Å O-Al-P, 169 -
174
Mitra, DePue, Parkin, Atwood, J. Am. Chem. Soc.
128 (2006) 1147.
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Dealkylation to Terminal Phosphinate
Al-O3, 2.026 Å Al-O4, 1.873 Å O-Al-O,
175 Al-O-P, 151
Mitra, Parkin, Atwood, Inorg. Chem. 45 (2006)
3970.
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Phosphate-Bridged Dealkylated Compound
Al-O, 1.82-1.88Å Al-O-P, 165 O-P-O, 110
Mitra, Parkin, Atwood, Inorg. Chem. 45 (2006)
3970.
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Salpen(tBu)AlOP(O)(H)Ph2
Wang, Parkin, Atwood, Inorg. Chem. 41 (2002) 558
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Structure of Salen(tBu)AlOP(O)(H)Ph8
Wang, Parkin, Atwood, Inorg. Chem. 41 (2002) 558
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Catalytic Dealkylation with BBr3
Mitra, DePue, Parkin, Atwood, J. Am. Chem.
Soc. 128 (2006) 1147.
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Problematic Phosphate Esters
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Deactivation of Actual Nerve Gas Agents -
Preliminary Results
Unpublished Results. Prof. Dan Williams,
KSU Conducted at the Aberdeen Proving Grounds, MD
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Discussing Study Results
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Nerve Agent Filtration-Deactivation Through
Covalent Bonding
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Conclusions and Continued Work

• Dealkylation of Phosphate Esters
• LBX (X Br)
• Salen(BX2)2
• Salen(BPhX)2
• SalenAlBr
• Bromides Most Effective
• Cationic Intermediates
• Dinuclear Compounds not Necessary
• Characterization of (SalenAl)3(PO4) Products
• Characterization of (SalenB2)3(PO4)4 Products
• Characterization of Partial Dealkylation
  Intermediates
• Salan(BBr)2 Too Air Sensitive (not described)