Created byThomas Avila ([email protected]), Mark Hendricks and Camille Sultana and posted on VIPEr on December 2009. Copyright Thomas Avila 2009. This work is licensed under the Creative Commons Attribution Non-commercial Share Alike License. To view a copy of this license visit http://creativecommons.org/about/license/ . This document was created as part of the requirements for Chemistry 165 "Organometallics" at Harvey Mudd College during the fall semester 2009. Student groups were asked to collaboratively research and prepare an extensive literature review on an organometallic topic. Some of these topics were introduced in class; If so, they were expected to extend beyond the specific metal or system discussed in class. Each presentation went through two rounds of peer review.
Transcript
Created byThomas Avila ([email protected]), Mark Hendricks and Camille Sultana and posted on VIPEr on December 2009. Copyright Thomas Avila 2009. This work is licensed under the Creative Commons Attribution Non-commercial Share Alike License. To view a copy of this license visit http://creativecommons.org/about/license/.
This document was created as part of the requirements for Chemistry 165 "Organometallics" at Harvey Mudd College during the fall semester 2009. Student groups were asked to collaboratively research and prepare an extensive literature review on an organometallic topic. Some of these topics were introduced in class; If so, they were expected to extend beyond the specific metal or system discussed in class. Each presentation went through two rounds of peer review.
Created byThomas Avila ([email protected]), Mark Hendricks and Camille Sultana and posted on VIPEr on December 2009. Copyright Thomas Avila 2009. This work is licensed under the Creative Commons Attribution Non-commercial Share Alike License. To view a copy of this license visit http://creativecommons.org/about/license/.
Metal and “Noble” Gas Interactions:A History of Unexpected Chemistry
Chemistry 165
Mark Hendricks, Thomas Avila, and Camille Sultana
http://eng.reklamballonger.se/helium.php
(watermarked in background)
Created byThomas Avila ([email protected]), Mark Hendricks and Camille Sultana and posted on VIPEr on December 2009. Copyright Thomas Avila 2009. This work is licensed under the Creative Commons Attribution Non-commercial Share Alike License. To view a copy of this license visit http://creativecommons.org/about/license/.
Created byThomas Avila ([email protected]), Mark Hendricks and Camille Sultana and posted on VIPEr on December 2009. Copyright Thomas Avila 2009. This work is licensed under the Creative Commons Attribution Non-commercial Share Alike License. To view a copy of this license visit http://creativecommons.org/about/license/.
Noble Gases: What’s in a Name?
Linus Pauling
The Nature of the Chemical Bond. IV. The Energy of Single Bonds and the Relative Electronegativity of Atoms (1932)
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The First of Its Kind:Xenon Hexafluoroplatinate
Neil Bartlett
Xe + PtF6 XePtF6
•Motivated by O2+[PtF6]-
•Concluded 1:1 Xe+[PtF6]-
Modern Conclusions
Bartlett, N. “Xenon Hexafluoroplatinate(V) Xe+
[PtF6]-”. Proceedings of the Chemical Society of London, 1962, (JUN), 218-&.
picture of Neil Bartlett
Created byThomas Avila ([email protected]), Mark Hendricks and Camille Sultana and posted on VIPEr on December 2009. Copyright Thomas Avila 2009. This work is licensed under the Creative Commons Attribution Non-commercial Share Alike License. To view a copy of this license visit http://creativecommons.org/about/license/.
Matrix Isolation Studies: M-NG?
• Studied matrix (solvent) effects of M(CO)5 spectra
• First systematic study of noble gas coordination to transition metal center
• Introduced possibility of NG-metal bonds
Perutz, R. N.; Turner, J. “Photochemistry of the Group 6 Hexacarbonyls in Low-Temperature Matrices. III. Interaction of the Pentacarbonyls with Noble Gases and Other Matrices”. J. Journal of the American Chemical Society, 1975, 97 (17), 4791-4800.
Robin Perutz (U. of York)
Figure 8 (from Journal of the American Chemical Society, 1975, 97 (17), 4791-4800)
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Matrix Isolation Studies
Mixed Matrix study: Visible spectra of Cr(CO)5 in Ne-2% Xe matrix
Figure 1 (from Journal of the American Chemical Society, 1975, 97 (17), 4791-4800)
Figure 4 (from Journal of the American Chemical Society, 1975, 97 (17), 4791-4800)
Created byThomas Avila ([email protected]), Mark Hendricks and Camille Sultana and posted on VIPEr on December 2009. Copyright Thomas Avila 2009. This work is licensed under the Creative Commons Attribution Non-commercial Share Alike License. To view a copy of this license visit http://creativecommons.org/about/license/.
XeF2: A Noble Ligand
Unit cell of [Ag(XeF2)2]AsF6
Hagiwara, R et al. “The crystal structure of [Ag(XeF2)2]AsF6
”. Eur. J. Solid State Inorg. Chem., 1991, 28, 855-866.
• First time XeF2 used as a ligand to a metal center
•coordinated through fluorines
•Prepared from solution of XeF2 and AgAsF6 in HF or a melt of AgAsF6 in liquid XeF2.
Figure 1 (from Eur. J. Solid State Inorg. Chem., 1991, 28, 855-866)
Created byThomas Avila ([email protected]), Mark Hendricks and Camille Sultana and posted on VIPEr on December 2009. Copyright Thomas Avila 2009. This work is licensed under the Creative Commons Attribution Non-commercial Share Alike License. To view a copy of this license visit http://creativecommons.org/about/license/.
XeF2: Further advances
• First compound with a metal center in a homoleptic environment of XeF2 molecules
• Crystallographic and Raman spectroscopy analysis
• Two unique calcium atom centers
Boris Žemva (Jožef Stefan Institute )
Ca2(AsF6)2excess (n>20) XeF2
aHFCa2(XeF2)9(AsF6)4
Tramsek, M.; Benkic, P.; Zemva, B. “The First Compound Containing a Metal Center in a Homoleptic Environment of XeF2 molecules”. Angew. Chem. Int. Ed. 2004, 43, 3456-3458.
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XeF2: Further advances
Homoleptic calcium center (9 XeF2 ligands) Second calcium center
Created byThomas Avila ([email protected]), Mark Hendricks and Camille Sultana and posted on VIPEr on December 2009. Copyright Thomas Avila 2009. This work is licensed under the Creative Commons Attribution Non-commercial Share Alike License. To view a copy of this license visit http://creativecommons.org/about/license/.
Michael Gerry (U. of British Columbia)
Composite spectrum of J = 6 – 5 transition of Ar-AgCl
• Studies of Ar-AgX (X = F, Cl, Br) with microwave spectroscopy
• Based on fundamental stretching frequency and length of Ar-Ag interaction conclude that Ar-Ag interaction is more than a van der Waals complex
Evans, Corey J., Gerry, Michael C. L. “The Microwave Spectra and Structures of Ar-AgX (X = F, Cl, Br)”. Journal of Chemical Physics 112 (2000): 1321-1329.
New Techniques
Figure 1
(from Journal of Chemical Physics 112 (2000): 1321-1329)
http://www.chem.ubc.ca/personnel/faculty/gerry/
(pic at top left)
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Michael George (U. of Nottingham)
• Kinetics studies of CO substitution in (η5-C5R5)M(CO)2L (M = Mn or Re; R = H, Me, or Et (Mn only); L = Kr or Xe) complexes
Grills, David C., Sun, Xue Z., Childs, Gavin I., George, Michael W. “An Investigation into the Reactivity of Organometallic Noble Gas Complexes: A Time-Resolved Infrared Study in Supercritical Noble Gas and Alkane Solution at Room Temperature”. Journal of Physical Chemistry A 104 (2000), 4300-4307.
Probing Reactivity
Figure 5
(from Journal of Physical Chemistry A 104 (2000), 4300-4307)
Figure 6
(from Journal of Physical Chemistry A 104 (2000), 4300-4307)
Created byThomas Avila ([email protected]), Mark Hendricks and Camille Sultana and posted on VIPEr on December 2009. Copyright Thomas Avila 2009. This work is licensed under the Creative Commons Attribution Non-commercial Share Alike License. To view a copy of this license visit http://creativecommons.org/about/license/.
M-Ng Bonds: Room for Theory
Prof. Pekka Pyykkö (University of Helsinki)
1995: Published Predicted Chemical Bonds between Rare Gases and Au+
First paper theorizing the stability of the Noble gas – gold ion bond
Results suggest that He and Ne would form weak complexes with Au+, while Kr and Xe would form stronger bonds with increasing covalent character
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Konrad Seppelt (Free U. of Berlin)
• Synthesis of the first isolable noble gas-metal complex (2000)
• AuXe42+(Sb2F11
-)2
• First X-ray crystallographic data collected on noble gas-metal complexes
• Measured properties match well with theoretical predictions
Seidel, Stefan, Seppelt, Konrad. “Xenon as a Complex Ligand: The Tetra Xenono Gold(II) Cation in AuXe4
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Bruce Bursten (The Ohio State University)
Li, Jun, Bursten, Bruce E., Liang, Binyong, Andrews, Lester. “Noble Gas-Actinide Compounds: Complexation of the CUO Molecule by Ar, Kr, and Xe Atoms in Noble Gas Matrices”. Science 295 (2002): 2242-2245.
• First observation of noble gas-actinide complex (Ng-CUO; Ng = Ar, Kr, Xe)
• Authors conclude that interaction is true chemical bond between noble gas and uranium
New Directions
A: IR spectra of CUO in Ne matrixB: IR spectra of CUO in Ne matrix doped with 1% ArC: IR spectra of CUO in Ar matrix(all with peak assignations)
Figure 2
(from Science 295 (2002): 2242-2245)
Figure 1
(from Science 295 (2002): 2242-2245)http://
www.brucebursten.com/
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M-Ng Bonds: More Room for Theory
2008: Published Evidence for Emergent Chemical Bonding in Au+-Ng Complexes (Ng = Ne, Ar, Kr, and Xe)
Prof. Breckenridge (University of Utah)
So, Are the Ng-Au Bonds Covalent Bonds or Not?
Insert table 2 from:
Breckenridge, W. H.; Ayles, V. L.; Wright, T. G., Journal of Physical Chemistry A 2008, 112 (18), 4209-4214.
Created byThomas Avila ([email protected]), Mark Hendricks and Camille Sultana and posted on VIPEr on December 2009. Copyright Thomas Avila 2009. This work is licensed under the Creative Commons Attribution Non-commercial Share Alike License. To view a copy of this license visit http://creativecommons.org/about/license/.
M-Ng Bonds: More Room for Theory2008: Published The Chemical Bond between Au(I) and the Noble Gases.
Comparative Study of NgAuF and NgAu+ (Ng = Ar, Kr, Xe) by Density Functional and Coupled Cluster Methods
Plot of computed dissociation energies with various theoretical models.
Insert figure 1 from:
Belpassi, L.; Infante, I.; Tarantelli, F.; Visscher, L., Journal of the American Chemical Society 2008, 130 (3), 1048-1060.
Created byThomas Avila ([email protected]), Mark Hendricks and Camille Sultana and posted on VIPEr on December 2009. Copyright Thomas Avila 2009. This work is licensed under the Creative Commons Attribution Non-commercial Share Alike License. To view a copy of this license visit http://creativecommons.org/about/license/.
M-Ng Bonds: More Room for Theory2008: Published The Chemical Bond between Au(I) and the Noble Gases.
Comparative Study of NgAuF and NgAu+ (Ng = Ar, Kr, Xe) by Density Functional and Coupled Cluster Methods
DC-CCSD(T) potential energy curves along the KrAu distance for KrAu+ and KrAuF. For the latter, the AuF bond length is kept fixed at theequilibrium value.
Contour plots of the electron density of AuF (black) and Au+ (red). The contour levels are 0.01 - 0.06e/au3 with a step of 0.01. Distances are in Å.
Insert figure 2 from:
Belpassi, L.; Infante, I.; Tarantelli, F.; Visscher, L., Journal of the American Chemical Society 2008, 130 (3), 1048-1060.
Insert figure 3 from:
Belpassi, L.; Infante, I.; Tarantelli, F.; Visscher, L., Journal of the American Chemical Society 2008, 130 (3), 1048-1060.
Created byThomas Avila ([email protected]), Mark Hendricks and Camille Sultana and posted on VIPEr on December 2009. Copyright Thomas Avila 2009. This work is licensed under the Creative Commons Attribution Non-commercial Share Alike License. To view a copy of this license visit http://creativecommons.org/about/license/.
The Players,
So Far…(A) Hermann J. Frohn; (B) Dieter Naumann; (C) Gary J. Schrobilgen; (D) Konrad Seppelt; (E) Michael C. L. Gerry; (F) Markku Rasanen; (G) Boris Zemva; (H) Neil Bartlett; (I) Lester Andrews; (J) John H. Holloway; (K) Pekka Pyykko; (L) Benny J. Gerber
Nobel Gas ChemistryInsert figure 11 from:
Grochala, W., Atypical compounds of gases, which have been called 'noble'. Chemical Society Reviews 2007, 36 (10), 1632-1655.
Created byThomas Avila ([email protected]), Mark Hendricks and Camille Sultana and posted on VIPEr on December 2009. Copyright Thomas Avila 2009. This work is licensed under the Creative Commons Attribution Non-commercial Share Alike License. To view a copy of this license visit http://creativecommons.org/about/license/.
Nobel Gas Chemistry
Where We’ve Been
Where We’re Going
50 Years of Noble Gas Chemistry
Insert figure 10 from:
Grochala, W., Atypical compounds of gases, which have been called 'noble'. Chemical Society Reviews 2007, 36 (10), 1632-1655.
(and move to back in PowerPoint to put arrow on top of figure)
