Prof. Tom Ziegler Department of Chemistry

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Tuesday February 19 at 11.00 a.m.
Prof. Tom Ziegler - Department of
Chemistry University of Calgary-Calgary,Alberta,Ca
nada T2N 1N4
"Density Functional Theory as a Practical Tool in
Transition Metal Chemistry"
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More than 1000 atoms possible
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17O shieldings in transition metal oxides MO4n-

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Results I scalar ZORA
W(CO)6 W(CO)5PF3W(CO)5PCl3W(CO)5WI3cp-W(CO)3HW
F6
Tungsten compounds
J.Autschbach , T. Ziegler, JCP (2000), in press

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Results I scalar ZORA
Mercury compounds
CH3HgCH3 CH3HgCl CH3HgBr CH3HgIHg(CN)2
Hg(CN)42-
J.Autschbach , T. Ziegler, JCP (2000), in press
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Results III solvent effects
NMR experiments usually in solution, ?
Coordination by solvent
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Results III solvent effects
) Hg-C coupling, VWN functional
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Results I scalar ZORA
Pt(PF3)4
Platinum compounds
cis-PtCl2(P(CH3)3)2trans-PtCl2(P(CH3)3)2cis-PtH2
(P(CH3)3)2 trans-PtH2(P(CH3)3)2 Pt(P(CH3)3)4
Pt(PF3)4
J.Autschbach , T. Ziegler, JCP (2000), in
press
PtX2(P(CH3)2)
J.Autschbach , T. Ziegler, JCP (2000), in press

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Results III solvent effects
cis-PtH2(PMe3)2 Knrel 908 Krel 1018 SO
1136 Exp. 1786 ? 1019 kg/m2C2 )
K 1537
K 1551
) Pt-P coupling, VWN functional
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Results Main group diatomics
Main-group diatomics
NI, 3?
SO, 3?
NH, 3?
B2, 3?
PH, 3?
Ge2, 4?
O2, 3?
SiB, 4?
BC, 4?
AlC, 4?
SeO, 3?
C2, 4?
SiAl, 4?
Si2, 4?
S2, 3?
Ge2, 4?
GaAs, 4?
Gas-phase value
The gas-phase experimental values (circled) for
?g? were computed from microwave spectral
parameters using Curl equation13. The remaining
experimental values are noble gas matrices. In
all cases, the parallel component ?g is close
to the free electron value, both in theory and in
experiment
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Main group-transition metal diatomics
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MnI, 7?
MnO, 6?
MnBr, 7?
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MnCl, 7?
MnS, 6?
MnH, 7?
0
MoN, 4?
CrH, 6?
CrN, 4?
-20
Calculated ?g ? (BP86)
MnF, 7?
NbO, 4?
-40
VO, 4?
Gas-phase value
YAl, 4?
CrF, 6?
YB, 4?
-60
Experimental ?g?, parts per thousand (ppt)
-80
-80
-60
-40
-20
0
20
40
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Transition metal-transition metal diatomics
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HCN ? CNH isomerisation
CNH
HCN
TS
IRP
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HCN ? CNH isomerisation
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SN2 reaction Cl- CH3Cl ? Cl-CH3 Cl-
Cl- CH3Cl
TS
Cl-CH3 Cl-
IRP (TS ? P)
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Typical Polymerization System
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Traditional Computational Models
gas phase model system
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A QM/MM study of Monomer Capture in Brookharts
Catalyst
RH
RMe
indirect steric effect
R substituent effect found to be both electronic
and steric effect
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NMR/ESR
The Heavy Metal Band
Georg Schreckenbach
Steve Wolff
Yosadara Morales
Sergei Patchkovskii
Jochen Autschbach
Jana Khandogin
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Catalyses and Dynamics
Eva Zurek
Peter Margl
Mary Chan
Artur Michalak
Liqun Deng
Tom Woo
Kumar Vanka
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