a pyrophoric affair
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A Pyrophoric Affair
Phosphorus Chemistry forthe New Millenium
Hennig Brand Discovers Phosphorus
painting by Joseph Wright, 1771
PP
P
P
A Molecule of the White (Yellow) Allotrope of Phosphorus
Phosphorus Chemistry
Current Students:Ryan Nelson, Jeff Johnson,Chris Krug, Yong Soo Hoo
Osmium, Rhenium, and Ruthenium Chemistry
Current Student:Travis McKenzie
Our Current Research Areas
Other Research Areas
Buckminsterfullerene (C60) Chemistry
Synthesis of Aminophenytoin
Development of New Organic & InorganicLaboratory Experiments
Current Senior Gustavus Phosphorus Chemists
Ryan Nelson Jeff Johnson
PR
R
R
Bonding of a Phosphine to a Metal Atom Attached to <n> Other Ligands
M M
R
RR
PLn Ln
Industrial Synthesis of L-DOPA
+
Catalysis of Hydrogen Addition to a Carbon-Carbon Double Bond in One Step of the Industrial Synthesis of L-Dopa
H2
Rh
OCH3
PP
OCH3
CC
CO2H
NHCOCH3
OCH3
CH3CO2
H
CC
CO2H
NHCOCH3
OCH3
CH3CO2
H
H
H
General Structure of a Phthaloylphosphine (lone electron pairs on O and P not shown)
65
4
32
1
C
CC
C
CC C
PC
O
O
H
H
H
H
R
1. Synthesis of the Organic Backbones
2. Preparation and Characterization (NMR, IR, elemental analysis) of the Phosphorus(III) Anions
3. Exploration of the Chemistry of the Phosphorus(III) Anions and their Derivatives
Phthaloylphosphide Projects - Overview
Preparation of the Potassium/18-crown-6 Salt of t-Butylphthaloylphosphide
t-butyl chloride
zinc chloride catalyst
H2O, pyridineKMnO4,1)
2) H3O+
CO2H
CO2H
CO2H
CO2H
CH3CH2OH, H2SO4
CO2CH2CH3
CO2CH2CH3
CO2CH2CH3
CO2CH2CH3
PH3, K+CH3CH2(CH3)2CO-
CH3CH2(CH3)2COH18-crown-6
P-
O
O
G = 4- or 4,5- substituent
G
PH3
CsOC(CH3)2CH2CH3, CH3CH2(CH3)2COHG
O
OCH2CH3
O
OCH2CH3
_P
O
O
General Synthetic Procedure for Phthaloylphosphides CsPH 2 is generated by reaction of PH3 with the cesium t-amyloxide base.
+ 2CH3CH2OH
__
___
A Selection of Phthaloylphosphide Ions
P
O
O
P
O
O
F3C
F3C
N
P
O
O
P
O
OC
H2C
H2CC
CH3CH3
CH3 CH3
P
O
OF3C
P
O
O
P
O
O
P
O
O
P
O
O
Bidentate Phthaloylphosphine LigandsPrepared from Phthaloylphosphide
P
O
O
_
31P NMR spectrum
N
P
O
O
_
13C NMRspectrum
Ryan Performing a Schlenk line filtration
Ryan working in the glove box
Jeff Operating the300 MHz Multinuclear
NMR Spectrometer
NMR Spectrometer Fundedby NSF, Dreyfus, & GAC
Future Research Directions
1. Quantification of the physical and chemical properties of the phthaloylphosphides and their derivatives2. Exploration of the ligand behavior of the phthaloylphosphides and their derivatives3. Use of phthaloylphosphides in preparation of R-PH2
(R = organic group)4. New preparation of P2H4 via phthaloylphosphide5. Preparation of new organic conductors via polyfunctional phthaloylphosphides...
PR
R
R
Bonding of a Phosphine to a Metal Atom Attached to <n> Other Ligands
M M
R
RR
PLn Ln
P
PPO
O
Pt
O
OP
A Platinum Complex of a Bidentate Phthaloylphosphine Ligand
_P
O
O
Cs+
+
Reagent for preparation of primary alkyl phosphines
R X
alkyl halideP
O
O
R R PH2
Future Projects
G = H, 4-, or 4,5- substituent
_P
O
O
G
Future Projects
Hammett linear free energy rate study for the series ofmonosubstituted phthaloylphosphides
Cyclic voltammetry studies of the same series
Cs+
_P
O
O
Cs+
+
TlF3CO OCCF3
OO
TlPP
TlPP
+PH2
Reagent for preparation of primary aryl phosphines
CO2Et
CO2EtEtO2C
EtO2C
PP
O
O
O
O
__
PP
O
O
O
O
CN
CNNC
NC
+. _.PP
O
O
O
O
G+
?
CH3I
TCNQ
?
AsAs
O
O
O
O
PAs
O
O
O
O
Charge-Transfer to formOrganic Conductors?
Some Scenes from Our Research Laboratory
Jeff Johnson, Brian O’Brien,and Ryan Nelson, Summer 1998
Student Stipends provided by theACS Division of Fluorine Chemistry (Jeff)and Gustavus Adolphus College (Ryan,Presidential Student/Faculty Research Grant)
Research GroupMeeting, Summer 1998
Views of Laboratory Operations
Preparation of OurPrimary Starting Material
Ryan and Cesium
Items Fromthe Heavenly
Bakery
?PP
OO
PP
O
O
__ _ _
CO2Et KPH2
O
PH_
K +
O
PH2
HO
P
O
- PH3
Preparation of Dibenzoylphosphine
CF3CO2H
An Assortment of Inspirational Substances
CF3N3 (CF 3)2C=C=O CS P 2 C2 S2
CSe2 COSe (HCF 2CF2)2PH HCF 2CF2PH2 OsO4
F2C P
CF3F C P
Se Se
F3C CF3
F C NF3C C
N Br
FC N
-O3S
-O3S
N+ -
F C C F
F C C H F3C C C H
F C C-F3C C C
-
O C C C O
Si
N N N+ -
N N N+ -
N N N+ -
N Si+ -
C C F
F
F
F
F
FF
Os
N
N
H
H
O
N
N
H
H
The End
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