Outline Background Project Goals Preliminary Results Summary Future Work

Examining Unsupported Heterogenous

Metal-Metal bonding in the F-Block:
Lanthanide-Metal and Actinide-Metal bonds

Bess Vlaisavljevich

25 February 2010

Bess Vlaisavljevich
25 Feb 2010
Outline Background Project Goals Preliminary Results Summary Future Work

1 Background

2 Project Goals

3 Preliminary Results
DFT Results
CASPT2 Results

4 Summary

5 Future Work

Bess Vlaisavljevich
25 Feb 2010
Outline Background Project Goals Preliminary Results Summary Future Work

How common are these types of bonds?

Experimentally Determined
Lanthanide Containing Bonds
Total 48
Actinide Containing Bonds
Total 15
With Unsupported Bonds 9

Liddle and Mills, Dalton Trans., 2009,5592-5605

Bess Vlaisavljevich
25 Feb 2010
Outline Background Project Goals Preliminary Results Summary Future Work

Project Goals

Find La-M and Ac-M bonds with “equivalent” ligand

environments

Bess Vlaisavljevich
25 Feb 2010
Outline Background Project Goals Preliminary Results Summary Future Work

Project Goals

Find La-M and Ac-M bonds with “equivalent” ligand

environments
Study the electronic structure of the bonds

Bess Vlaisavljevich
25 Feb 2010
Outline Background Project Goals Preliminary Results Summary Future Work

Project Goals

Find La-M and Ac-M bonds with “equivalent” ligand

environments
Study the electronic structure of the bonds
Compare bonding in Ac to the La

Bess Vlaisavljevich
25 Feb 2010
Outline Background Project Goals Preliminary Results Summary Future Work

Project Goals

Find La-M and Ac-M bonds with “equivalent” ligand

environments
Study the electronic structure of the bonds
Compare bonding in Ac to the La
Hopefully establish trends and predict structures yet to be
synthesized

Bess Vlaisavljevich
25 Feb 2010
Outline Background Project Goals Preliminary Results Summary Future Work

Unsupported Hererodinuclear Bonds Containing Actinides

Nine Complexes Characterized Experimentally

[Th(η 5 -C5 H5 )2 (I)Ru(η 5 -C5 H5 )(CO)2 ]
[{N(CH2 CH2 NSiMe3 )3 }URe(η 5 -C5 H5 )2 ]
[U(η 5 -C5 H4 SiMe3 )3 {Al(η 5 -C5 Me5 )}]
[(TrenTMS )U{Ga(NArCH)2 }(THF)]
[(η 5 -C5 H5 )3 UGa(η 5 -C5 Me5 )]
[{(3,5-Me2 C6 H3 )N(Bu’)}3 U({Si(SiMe3 )3 }]
[(η 5 -C5 H5 )3 U(SiPh3 )]
[(η 5 -C5 H5 )3 U(GePh3 )]
[(η 5 -C5 H5 )3 U(SnPh3 )]

Bess Vlaisavljevich
25 Feb 2010
Outline Background Project Goals Preliminary Results Summary Future Work

Unsupported Hererodinuclear Bonds Containing Actinides

We are currently studying those in blue

[Th(η 5 -C5 H5 )2 (I)Ru(η 5 -C5 H5 )(CO)2 ]
[{N(CH2 CH2 NSiMe3 )3 }URe(η 5 -C5 H5 )2 ]
[U(η 5 -C5 H4 SiMe3 )3 {Al(η 5 -C5 Me5 )}]
[(TrenTMS )U{Ga(NArCH)2 }(THF)]
[(η 5 -C5 H5 )3 UGa(η 5 -C5 Me5 )]
[{(3,5-Me2 C6 H3 )N(Bu’)}3 U({Si(SiMe3 )3 }]
[(η 5 -C5 H5 )3 U(SiPh3 )]
[(η 5 -C5 H5 )3 U(GePh3 )]
[(η 5 -C5 H5 )3 U(SnPh3 )]

Bess Vlaisavljevich
25 Feb 2010
Outline Background Project Goals Preliminary Results Summary Future Work

“Equivalent” Lanthanide Complexes

[(η 5 -C5 H5 )2 Lu(THF)Ru(η 5 -C5 H5 )(CO)2 ]

[(η 5 -C5 H5 )2 YRe(η 5 -C5 H5 )2 ]
[Y{Ga(NArCh)2 }{C(PPh2 NSiMe3 )2 }(THF)2 ]
[Tm{Ga(NArCH)2 }{(NArCH)2 }(tmeda)]
[Yb(η 5 -C5 Me5 ){Si(SiMe3 )3 (THF)2 }]

Bess Vlaisavljevich
25 Feb 2010
Outline Background Project Goals Preliminary Results Summary Future Work

DFT Results

Strategy Taken

Start from crystal structure or coordinates from previous

calculations (when available)
Optimized the geometry with Turbomole
PBE functional and def2-TZVPP(for H-Rn)/def-TZVPP(for
La-U) basis sets were used

Bess Vlaisavljevich
25 Feb 2010
Outline Background Project Goals Preliminary Results Summary Future Work

DFT Results

Optimized Metal-Metal Bond Distances in Å

Two Metals PBE Distance Experimental Distance
Th Ru 3.064 3.028
U Re 3.043 3.048
U Ga (one) 3.162 3.221/3.298
U Ga (two) 3.065/3.080
U Si N/A
U Sn 3.166
Lu Ru 3.015 2.995
Y Re 3.000 2.962
Y Ga 3.120 2.935
Tm Ga 2.974
Yb Si 3.002 3.032
*blank spaces in table for calculations currently underway
Bess Vlaisavljevich
25 Feb 2010
Outline Background Project Goals Preliminary Results Summary Future Work

CASPT2 Results

Strategy Taken
Once the PBE geometry was determined and deemed
reasonable in comparison with experimental results,
CASSCF/CASPT2 calculations were performed

Bess Vlaisavljevich
25 Feb 2010
Outline Background Project Goals Preliminary Results Summary Future Work

CASPT2 Results

Strategy Taken
Once the PBE geometry was determined and deemed
reasonable in comparison with experimental results,
CASSCF/CASPT2 calculations were performed
First, I considered what the expected the oxidation state of
each metal would be

Bess Vlaisavljevich
25 Feb 2010
Outline Background Project Goals Preliminary Results Summary Future Work

CASPT2 Results

Strategy Taken
Once the PBE geometry was determined and deemed
reasonable in comparison with experimental results,
CASSCF/CASPT2 calculations were performed
First, I considered what the expected the oxidation state of
each metal would be
Ran an SCF calculation

Bess Vlaisavljevich
25 Feb 2010
Outline Background Project Goals Preliminary Results Summary Future Work

CASPT2 Results

Strategy Taken
Once the PBE geometry was determined and deemed
reasonable in comparison with experimental results,
CASSCF/CASPT2 calculations were performed
First, I considered what the expected the oxidation state of
each metal would be
Ran an SCF calculation
From the SCF results, an active space was chosen using the
ANO-RCC-MB basis set

Bess Vlaisavljevich
25 Feb 2010
Outline Background Project Goals Preliminary Results Summary Future Work

CASPT2 Results

Strategy Taken
Once the PBE geometry was determined and deemed
reasonable in comparison with experimental results,
CASSCF/CASPT2 calculations were performed
First, I considered what the expected the oxidation state of
each metal would be
Ran an SCF calculation
From the SCF results, an active space was chosen using the
ANO-RCC-MB basis set
Once I was happy with the AS, I moved to a larger basis set
VTZP for Metals
VDZP for ligand atoms directly interacting with the metals
MB for the remaining atoms

Bess Vlaisavljevich
25 Feb 2010
Outline Background Project Goals Preliminary Results Summary Future Work

CASPT2 Results

Strategy Taken
Once the PBE geometry was determined and deemed
reasonable in comparison with experimental results,
CASSCF/CASPT2 calculations were performed
First, I considered what the expected the oxidation state of
each metal would be
Ran an SCF calculation
From the SCF results, an active space was chosen using the
ANO-RCC-MB basis set
Once I was happy with the AS, I moved to a larger basis set
VTZP for Metals
VDZP for ligand atoms directly interacting with the metals
MB for the remaining atoms
Optimize the M-M bond distance by hand
Bess Vlaisavljevich
25 Feb 2010
Outline Background Project Goals Preliminary Results Summary Future Work

CASPT2 Results

Consider a Neutral Diatomic M-M Bond

Metal Electron Configuration if neutral Active Space

Th Ru Th: 6d2 7s2 Ru: 4d7 5s1 (12,12)
U Re U: 7s1 6d2 5f3 Re: 4f14 5d5 6s2 (13,19)
U Ga U: 7s1 6d2 5f3 Ga: 4s2 4p1 (9,17)
Lu Ru Lu: 4f14 5d1 6s2 Ru: 4d7 5s1 (11,12)
Y Re Y: 4d1 5s2 Re: 4f14 5d5 6s2 (10,12)
Y Ga Y: 4d1 5s2 Ga: 4s2 4p1 (6,10)

Bess Vlaisavljevich
25 Feb 2010
Outline Background Project Goals Preliminary Results Summary Future Work

CASPT2 Results

Consider the Ligands – Estimate an oxidation state

Structure Estimated Ox. State

[Th(η 5 -C5 H5 )2 (I)Ru(η 5 -C5 H5 )(CO)2 ] Th3+ Ru1+
[{N(CH2 CH2 NSiMe3 )3 }URe(η 5 -C5 H5 )2 ] U3+ Re2+
[(TrenTMS )U{Ga(NArCH)2 }(THF)] U3+ Ga2+
[(η 5 -C5 H5 )3 UGa(η 5 -C5 Me5 )] U3+ Ga1+
[(η -C5 H5 )2 Lu(THF)Ru(η 5 -C5 H5 )(CO)2 ]
5 Lu2+ Ru1+
[(η 5 -C5 H5 )2 YRe(η 5 -C5 H5 )2 ] Y2+ Re+2
[Y{Ga(NArCH)2 }{C(PPh2 NSiMe3 )2 }(THF)2 ] Y2+ Ga2+

Bess Vlaisavljevich
25 Feb 2010
Outline Background Project Goals Preliminary Results Summary Future Work

CASPT2 Results

First Active Space

Est. Ox. State “Neutral AS” Init. AS Best AS

Th3+ Ru1+ (12,12) (8,12)
U3+ Re2+ (13,19) (8,19) (8,12)
U3+ Ga2+ (9,17) (4,17) (4,8)
U3+ Ga1+ (9,17) (5,17)
Lu2+ Ru1+ (11,12) (8,12) (8,12)
Y2+ Re+2 (10,12) (6,12) (6,6)
Y2+ Ga2+ (6,10) (2,10) (6,6)

Bess Vlaisavljevich
25 Feb 2010
Outline Background Project Goals Preliminary Results Summary Future Work

CASPT2 Results

Determine the Ground State with the Larger Basis Set

Metals AS Ground State

U Re (8,12) triplet
U Ga (one) (4,8) triplet
Lu Ru (8,12) singlet
Y Re (6,6) singlet
Y Ga (6,6) singlet

Bess Vlaisavljevich
25 Feb 2010
Outline Background Project Goals Preliminary Results Summary Future Work

CASPT2 Results

Determine the Ground State with the Larger Basis Set

Metals AS Ground State

U Re (8,12) triplet
U Ga (one) (4,8) triplet
Lu Ru (8,12) singlet
Y Re (6,6) singlet
Y Ga (6,6) singlet
*Bonds are highly ionic although URe and YRe have a sigma
bonding/antibonding pair

Bess Vlaisavljevich
25 Feb 2010
Outline Background Project Goals Preliminary Results Summary Future Work

CASPT2 Results

Example: URe Active Space

!"#",&'
Bonding and
Antibonding
pair

!)#$%&'

Bess Vlaisavljevich
25 Feb 2010
Outline Background Project Goals Preliminary Results Summary Future Work

CASPT2 Results

Example: URe Active Space

!"#**&' !"#**&'

Unpaired
Electrons

!"#).&' !"#).&'

Bess Vlaisavljevich
25 Feb 2010
Outline Background Project Goals Preliminary Results Summary Future Work

CASPT2 Results

Optimized Bond Distances for the Ground States with

Larger Basis Set

Metals AS Bond Opt

U Re (8,12) 2.94
U Ga (one) (4,8) 3.03
Lu Ru (8,12) underway
Y Re (6,6) 3.00
Y Ga (6,6) 3.18

Bess Vlaisavljevich
25 Feb 2010
Outline Background Project Goals Preliminary Results Summary Future Work

Bond Distance Summary

Two Metals CASPT2 PBE Experiment

Th Ru 3.06 3.03
U Re 2.94 3.04 3.05
U Ga (one) 3.03 3.16 3.22/3.30
U Ga (two) 3.07/3.08
U Si N/A
U Sn 3.17
Lu Ru 3.02 3.00
Y Re 3.00 3.00 2.96
Y Ga 3.18 3.12 2.94
Tm Ga 2.97
Yb Si 3.00 3.03

Bess Vlaisavljevich
25 Feb 2010
Outline Background Project Goals Preliminary Results Summary Future Work

Future Work

Continue studying the different types of bonds. So far bonds

are ionic in many cases. To date only U Re and Y Re have
active orbitals that appear to contain a sigma
bonding/antibonding pair

Bess Vlaisavljevich
25 Feb 2010
Outline Background Project Goals Preliminary Results Summary Future Work

Future Work

Continue studying the different types of bonds. So far bonds

are ionic in many cases. To date only U Re and Y Re have
active orbitals that appear to contain a sigma
bonding/antibonding pair
Study group 15 and actinde bonding (no experimental
structures)

Bess Vlaisavljevich
25 Feb 2010
Outline Background Project Goals Preliminary Results Summary Future Work

Future Work

Continue studying the different types of bonds. So far bonds

are ionic in many cases. To date only U Re and Y Re have
active orbitals that appear to contain a sigma
bonding/antibonding pair
Study group 15 and actinde bonding (no experimental
structures)
Ivan is looking at the second U Ga complex using ADF

Bess Vlaisavljevich
25 Feb 2010
Outline Background Project Goals Preliminary Results Summary Future Work

Future Work

Continue studying the different types of bonds. So far bonds

are ionic in many cases. To date only U Re and Y Re have
active orbitals that appear to contain a sigma
bonding/antibonding pair
Study group 15 and actinde bonding (no experimental
structures)
Ivan is looking at the second U Ga complex using ADF
Perform calculations on diatomic M-M structures for
comparison

Bess Vlaisavljevich
25 Feb 2010
Outline Background Project Goals Preliminary Results Summary Future Work

Future Work

Questions and Suggestions?

Bess Vlaisavljevich
25 Feb 2010