Bez tytulu slajdu

1
 92nd Canadian Chemistry Conference and
Exhibition in Hamilton, ON, May 30 June 4,
2009 Symposium on Atoms in Molecules in honor
of R.F.W. Bader
McMaster-ABB163 1040 am Thursday June 4,
2009 Organizer(s) Paul Ayers and Cherif Matta

Molecules (fragments) in Molecules
Tom Ziegler Department of Chemistry University
of Calgary Calgary Alberta Canada
2
Artur Michalak
Mariusz P. Mitoraj
Jagiellonian University Cracow, Poland Department
of Theoretical Chemistry
3
Some comments on chemical bond
4
Some comments on chemical bond
5
time
6
The plan of presentation
1. ETS-NOCV scheme short theoretical background.
2. Selected applications of ETS-NOCV
-covalent, dative bonds in main group elements
and TM single,
-double, multiple, donor-acceptor.
-hydrogen bonds A-T, H2O-H2O dimers.
-agostic interactions in early and late
transition metals.
-trans-effect

• -metal surfaces

7
Short theoretical background
8
Short theoretical background
Mitoraj, M.P, Michalak A., Ziegler T. Journal of
Chemical Theory and Computation, 2009, 5 ,
962-975 .
9
Short theoretical background
Mitoraj, M.P, Michalak A., Ziegler T. Journal of
Chemical Theory and Computation, 2009, 5 ,
962-975 .
10
Short theoretical background
?El ?A?B
Mitoraj, M.P, Michalak A., Ziegler T. Journal of
Chemical Theory and Computation, 2009, 5 ,
962-975 .
11
Short theoretical background
Mitoraj, M.P, Michalak A., Ziegler T. Journal of
Chemical Theory and Computation, 2009, 5 ,
962-975 .
12
Short theoretical background
Mitoraj, M.P, Michalak A., Ziegler T. Journal of
Chemical Theory and Computation, 2009, 5 ,
962-975 .
13
Covalent bonds
14
Covalent bonds
XH3-XH3
15
Covalent bonds
CH2CH2
16
Covalent bonds
17
Covalent bonds
18
Covalent bonds
19
Covalent bonds
20
(No Transcript)
21
(No Transcript)
22
Multiple bonds-TM
23
Multiple bonds-TM
24
Multiple bonds-TM
25
Multiple bonds-TM
189.0 -24.1 1.88
26
Dative bonds
(CO)5CrCH2
27
Dative bonds
(CO)5CrCH2
28
Dative bonds
29
Dative bonds
Ni-anilinotropone -C2H4
30
Dative bonds
-23.3 kcal/mol
31
Dative bonds
Ni-anilinotropone -C2H4
-43.5 kcal/mol
32
Hydrogen bonds
kcal/mol, (BP86/TZ2P) A-T
?Eint -13.0
?Eorb -22.0
?EPauli 38.7
?Eprep 2.1
?Eelstat -31.9
?Etotal-experiment99 -12.1
?Etotal other theoretical results -13.2
?Eorb-22.0
Célia Fonseca Guerra, F. Matthias
Bickelhaupt, Jaap G. Snijders, and Evert Jan
BaerendsJ. Am. Chem. Soc., 2000, 122 (17), pp
41174128
33
Hydrogen bonds
?Eorb-22.0
34
Hydrogen bonds
Adenine-Thymine
?Eorb-22.0
35
Hydrogen bonds
Adenine-Thymine
?Eorb-22.0
36
Hydrogen bonds
Kcal/mol, (BP86/TZ2P) H2OH2O
?Etotal -4.5
?Eorb -4.2
?EPauli 7.7
?Edist 0.0
?Eelstat -8.0
?H-experiment -3.6 ? 0.5
37
Agostic interaction
..the agostic term is used to discuss the
various manifestations of covalent interactions
between carbonhydrogen groups and transition
metal centers in organometallic compounds, in
which a hydrogen atom is covalently bonded
simultaneously to both a carbon and to a
transition metal atom. M. Brookhart
the agostic interactions are characterized by
the distortion of an organometallic moiety which
brings an appended C-H bond into close proximity
with the metal center W. Scherer.
38
Agostic interaction

• Solution NMR Spectroscopy long timescale of the
  NMR
• experiment, the weak nature of interaction
  the fluxionality
• averages the changes between two or more CH
  bonds such
• that the effect is obscured.
• X-Ray Diffiraction, low scattering factor for
  hydrogen
• Vibrational Spectroscopy, reduction of frequency,
  ?(CH), coupling
• between the overtones ? masking the
  interaction.
• 4. Gas Electron Diffraction, EPR data

39
Agostic interaction
- How we can rationally tune/modify the agosctic
interaction ?
40
Agostic interaction
41
Agostic interaction
Pd-diimine n-Pr
Ni-diimine n-Pr
42
Agostic interaction
Ti(IV) based metallocene with n-Pr
43
Agostic interaction
Neutral based catalyst with n-Pr
44
Agostic interaction
45
Extended systems examples
P. Philipsen and E.J. Baerends J.Phys.Chem. B
110, 12470
46
Fragment basis interactions
P. Philipsen and E.J. Baerends J.Phys.Chem. B
110, 12470
47
Relief term the Fock matrix
P. Philipsen and E.J. Baerends J.Phys.Chem. B
110, 12470
48
Nitrogen on Tungsten
P. Philipsen and E.J. Baerends J.Phys.Chem. B
110, 12470
49
(No Transcript)
50
The plan of presentation
1. ETS-NOCV scheme short theoretical background.

• 2. Selected applications of ETS-NOCV
• covalent, dative bonds in main group elements and
  TM single,
• -double, multiple, donor-acceptor.
• hydrogen bonds A-T, H2O-H2O dimers.
• agostic interactions in early and late
  transition metals.
• -trans-effect
• -metal surfaces

51
On the Origin of the Trans-Influence in Square
Planar d8 Complexes. A Theoretical Study
Extensive kinetic and thermochemical studies on
square planar complexes of d8 metals (MNi, Pd,
Pt) have revealed that the M-L bond strength
strongly depends on the trans - ligand T (trans
influence) as does the barrier of substitution of
L by another ligand Y (trans effect).
Trans-effect
Trans-influence
52
The model system trans-Ni(Cl)2(NH3)Tn (n0, -1)
T- B(Me)2-, H-, CP-, CH2CH3-, CN-, HC?C-,
Cl-, F-, with n-1
T PF3, PH3, P(CH3)3,CO, with n0,
Trans-(effect)-influence
Trans-effect
Trans-influence
53
The total Ni-N bond energy decomposition in the
Ni(Cl)2Tn-NH3 systems
54
The contours of the deformation density (??) and
the contributions from the pairs of complementary
orbitals for Ni(Cl)3-1-NH3 system
55
The donation (?qd) and the back-donation (?qbd)
contributions to Ni-N bond in the nickel
complexes trans-Ni(Cl)2NH3Tn compared to ?Eorb.
a ?qd ?q1, see the previous picture b ?qbd ?q2
?q3 see the previous picture
56
PtCl2T- fragment
57
(No Transcript)
58
Orbital diagram for the formation of the Ni-NH3 ?
bond between Ni(Cl)2Tn and NH3 in the square
planar complex T(Cl)2Ni(NH3)n.
?-Ni dz2 C1?T
59
Percent contribution from ?-T to the LUMO of
nickel fragment Ni(Cl)2Tn together with the
Ni-N distances and the HOMO energies of neutral
ligands T.
a,b see the previous picture c the HOMO energy
of neutral ligands T d Ni-N bond length in Å
60
Pauli repulsion
P. Philipsen and E.J. Baerends J.Phys.Chem. B
110, 12470
61
Summary of Energy terms
62
Relief of Pauli repulsion
P. Philipsen and E.J. Baerends J.Phys.Chem. B
110, 12470
63
Relief Hoffmanns book
64
Agostic interaction
Ligandmethyl acrylate
65
Moving to Calgary Canada
66
Calgary Skyline
67
University of Calgary
68
Banff Rocky Mountain National Park
69
Fragment basis construction
Transformation via fragment orbitals
Three orthogonalization steps
1) Occupied-Occupied
2) Project out occupied space from virtual space
3) Virtual-Virtual
To be or not to be occupied
Orthogonalization and occupations per irrep
P. Philipsen and E.J. Baerends J.Phys.Chem. B
110, 12470