Iron Carbonyl Dianions Stabilized by the Indium tris(3,5-dimethyl)-1 Pyrazolylborate Moiety  Brandon Alexander Chemistry S...
What’s a Pyrazolylborate? <ul><li>-S. Trofimenko (DuPont) </li></ul><ul><ul><li>-Appeared 1966 </li></ul></ul><ul><li>-Tri...
What’s a Pyrazolylborate? <ul><li>-Why a pyrazolylborate? </li></ul><ul><li>Synthesis </li></ul>-1
Types of Pyrazolylborates <ul><li>Bis(Pyrazolylborate) </li></ul><ul><li>Tris(Pyrazolylborate) </li></ul><ul><li>Tetrakis(...
Synthesis of Pyrazolylborate -1 (Ex)  “ tris” ligand K[HB-pz 3 ] “ bis” ligand K[H 2 B-pz 3 ] -1 “ Tetrakis” Ligand K[B-pz...
Indium  tris ( 3 , 5 -dimethyl)-1Pyrazolylborate <ul><li>Adding the Metal Center </li></ul>3 4 5 - R  group selection
Adding the Metal Center Synthesis L=tris ligand, [HB(Me 2 -pz) 3 ] Reger, et. al.  Organometallics . 1994. -1
Indium Pyrazolylborate  <ul><li>Now we synthesized an Indium Pyrazolylborate </li></ul>Now what? -Reactivity <ul><li>Can r...
Reacting the In-pz <ul><li>Create Metal-Metal bonds with In-pz and Metal Carbonyl(s) </li></ul><ul><li>Metal Carbonyl Anio...
Metal Carbonyls <ul><li>Reger, et.al. explored metal-metal bonds with two metal carbonyl complexes. </li></ul><ul><li>Fe(C...
Synthesizing the Metal Carbonyls into a [2-] Dianion Naphthalene Na (s)  + -2 -CO <ul><li>Collman, J.P.  Accounts of Chemi...
-2 Naphthalene Na (s)  + Synthesizing the Metal Carbonyls into a [2-] Dianion -CO
Stability of Metal Carbonyl Anions <ul><li>Metal Carbonyl Anions are light and extremely heat sensitive.  </li></ul><ul><l...
Bringing it all Together <ul><li>Selected Indium Pyrazolylborate has been synthesized. </li></ul><ul><li>A set of [2-] met...
Bringing it all Together <ul><li>Reactivity of the Indium Pyrazolylborate and the Metal Carbonyl Anions </li></ul><ul><li>...
Bringing it all Together <ul><li>“ One Pot” Reaction </li></ul>L = tris ligand, [HB(Me 2 -pz) 3 ] (M-CO) x  = any [2- ]met...
Final Product Short Metal-Metal Bond <ul><li>[(HB(Me 2 -pz) 3 ]In-Fe(CO)  4 </li></ul><ul><li>“ Shortest  In-Fe bond to da...
Final Product Short Metal-Metal Bond <ul><li>[(HB(Me 2 -pz) 3 ]In-W(CO)  5 </li></ul><ul><li>“ First  In-W bond to be stru...
Expanding the use of In-pz with one (or more) Metal Carbonyl Anions <ul><li>Strong, et. al. have developed a potential hig...
Hierarchy  Diiron nonacarbonyl Fe 2 (CO) 9 Triiron Dodecacarbonyl Fe 3 (CO) 12 Iron pentacarbonyl* Diiron dianion [Fe 2 (C...
Synthesis of Diiron Nonacarbonyl <ul><li>Photolysis of Commercial Iron Pentacarbonyl </li></ul>2Fe(CO) 5 Fe 2 (CO) 8  + 2 ...
 
IR Analysis <ul><li>Carbonyl Peaks are comparable to Commercially available spectra and spectra from literature.  </li></ul>
 
Sigma-Aldrich FT-IR
Synthesis of Triethylenediamine octacarbonylferrate [Fe(C 2 H 4 (NH 2 ) 2 ) 3 ][(Fe 2 (CO) 8 ] <ul><li>Following Heiber, e...
Synthesis of Triethylenediamine octacarbonylferrate After rinsing the crystals with water, filtering and drying under vacu...
Synthesis of ([Hydrotris[(3,5 dimethylpyrazolyl)borato]indium]octacarbonyldiiron “ One Pot” Reaction + [Fe(C 2 H 4 (NH 2 )...
 
[Fe(en) 3 ][Fe 2 (CO) 8 ]
 
1 HNMR Results <ul><li>NMR spectroscopy of this compound provided an insight as to the structure of this compound. </li></...
 
 
1 HNMR (CD 3 SOCD 3 ): δ 5.505, 5.137 (s,s, 2.87, 2.09; 4-H); 3.388, 2.162 (m-m 18.89, 20.39; THF), 2.706, 1.883, (s-s, 45...
 
 
Synthesis of Triethylenediamine undodecacarbonyl ferrate <ul><li>[Fe(C 2 H 4 (NH 2 ) 2 ) 3 ][(Fe 3 (CO) 11 ] </li></ul><ul...
Synthesis of Triethylenediamine undodecacarbonyl ferrate After rinsing the crystals with water, filtering and drying under...
Synthesis of ([Hydrotris[(3,5 dimethylpyrazolyl)borato]indium] undodecacarbonyltriiron “ One Pot” Reaction + [Fe(C 2 H 4 (...
 
[Fe(en) 3 ][Fe 3 (CO) 11 ]
[HB(Me 2 -pz) 3 ][Fe 3 (CO) 11 ]
Gaussian Molecular Modeling <ul><li>Molecular Modeling Work using Gaussian can be used to predict gas phase IR  </li></ul>...
Conclusions <ul><li>Two different ethylenediamine derivatives of iron carbonyl dianions have been synthesized and the synt...
<ul><li>Two new iron metal carbonyl complexes have been coordinated to the Indium tris(3,5-dimethyl)-1 Pyrazolylborate Moi...
Further Research <ul><li>Gaussian Modeling to obtain gas phase IR </li></ul><ul><li>X-Ray Crystal Structures  </li></ul><u...
Acknowledgments <ul><li>Mount Union College  </li></ul><ul><li>Department of Chemistry </li></ul><ul><li>Dr. Scott Mason, ...
References <ul><li>Trofimenko, S. “Boron-Pyrazole Chemistry. II. Poly(1-pyrazolyl)borates”  J. Amer. Chem. Soc.  1967, 89 ...
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Iron Carbonyl Dianions Stablized By The Indium Tris(3,5 Dimethyl

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Iron Carbonyl Dianions Stablized By The Indium Tris(3,5 Dimethyl

  1. 1. Iron Carbonyl Dianions Stabilized by the Indium tris(3,5-dimethyl)-1 Pyrazolylborate Moiety Brandon Alexander Chemistry Seminar
  2. 2. What’s a Pyrazolylborate? <ul><li>-S. Trofimenko (DuPont) </li></ul><ul><ul><li>-Appeared 1966 </li></ul></ul><ul><li>-Tridentate </li></ul><ul><ul><li>-Can bind to a metal center with two donor sites like the pincers of a scorpion </li></ul></ul><ul><ul><li>-The third donor site reaches over the plane to bind to the final position created by the metal and the other two donor atoms </li></ul></ul><ul><ul><li>-Scorpionate Ligand </li></ul></ul><ul><ul><li>( fac manor) </li></ul></ul>1 -1
  3. 3. What’s a Pyrazolylborate? <ul><li>-Why a pyrazolylborate? </li></ul><ul><li>Synthesis </li></ul>-1
  4. 4. Types of Pyrazolylborates <ul><li>Bis(Pyrazolylborate) </li></ul><ul><li>Tris(Pyrazolylborate) </li></ul><ul><li>Tetrakis(Pyrazolylborate) </li></ul>-1 -1 -1
  5. 5. Synthesis of Pyrazolylborate -1 (Ex) “ tris” ligand K[HB-pz 3 ] “ bis” ligand K[H 2 B-pz 3 ] -1 “ Tetrakis” Ligand K[B-pz 4 ] Trofimenko, S. “ Boron-Pyrazole Chemistry. II. Poly(1-pyrazolyl)borates ” J. Amer. Chem. Soc. 1967, 89 , 3170. -1
  6. 6. Indium tris ( 3 , 5 -dimethyl)-1Pyrazolylborate <ul><li>Adding the Metal Center </li></ul>3 4 5 - R group selection
  7. 7. Adding the Metal Center Synthesis L=tris ligand, [HB(Me 2 -pz) 3 ] Reger, et. al. Organometallics . 1994. -1
  8. 8. Indium Pyrazolylborate <ul><li>Now we synthesized an Indium Pyrazolylborate </li></ul>Now what? -Reactivity <ul><li>Can react with </li></ul><ul><ul><li>Other pyrazolylborates </li></ul></ul><ul><ul><li>Diethyldithiocarbamate </li></ul></ul><ul><ul><ul><li>NaS 2 CN(C 2 H 5 ) 2 </li></ul></ul></ul><ul><ul><li>Maleonitriledithiolate </li></ul></ul><ul><ul><ul><li>MNT- ( Na 2 S 2 C 2 (CN) 2 ) </li></ul></ul></ul><ul><ul><li>Other R groups </li></ul></ul>Reger, et. al. Organometallics . 1994.
  9. 9. Reacting the In-pz <ul><li>Create Metal-Metal bonds with In-pz and Metal Carbonyl(s) </li></ul><ul><li>Metal Carbonyl Anions </li></ul>(In-pz= Indium Pyrazolylborate)
  10. 10. Metal Carbonyls <ul><li>Reger, et.al. explored metal-metal bonds with two metal carbonyl complexes. </li></ul><ul><li>Fe(CO) 5 </li></ul><ul><li>W(CO) 6 </li></ul>Reger, et. al. Organometallics . 1994.
  11. 11. Synthesizing the Metal Carbonyls into a [2-] Dianion Naphthalene Na (s) + -2 -CO <ul><li>Collman, J.P. Accounts of Chemical Research. 342-347. </li></ul>
  12. 12. -2 Naphthalene Na (s) + Synthesizing the Metal Carbonyls into a [2-] Dianion -CO
  13. 13. Stability of Metal Carbonyl Anions <ul><li>Metal Carbonyl Anions are light and extremely heat sensitive. </li></ul><ul><li>React violently with the atmosphere and readily release carbon monoxide. </li></ul><ul><li>Stored under Nitrogen environment </li></ul>
  14. 14. Bringing it all Together <ul><li>Selected Indium Pyrazolylborate has been synthesized. </li></ul><ul><li>A set of [2-] metal carbonyl anions have been synthesized </li></ul>-2 -2
  15. 15. Bringing it all Together <ul><li>Reactivity of the Indium Pyrazolylborate and the Metal Carbonyl Anions </li></ul><ul><li>“ One pot” reaction </li></ul>
  16. 16. Bringing it all Together <ul><li>“ One Pot” Reaction </li></ul>L = tris ligand, [HB(Me 2 -pz) 3 ] (M-CO) x = any [2- ]metal carbonyl <ul><li>Very High Molar Mass </li></ul><ul><li>Not very soluble </li></ul>Reger, et. al. Organometallics . 1994.
  17. 17. Final Product Short Metal-Metal Bond <ul><li>[(HB(Me 2 -pz) 3 ]In-Fe(CO) 4 </li></ul><ul><li>“ Shortest In-Fe bond to date” </li></ul>2.463(2) Å Reger, et. al. Organometallics . 1994.
  18. 18. Final Product Short Metal-Metal Bond <ul><li>[(HB(Me 2 -pz) 3 ]In-W(CO) 5 </li></ul><ul><li>“ First In-W bond to be structurally characterized” </li></ul>2.783(2) Å Reger, et. al. Organometallics . 1994.
  19. 19. Expanding the use of In-pz with one (or more) Metal Carbonyl Anions <ul><li>Strong, et. al. have developed a potential high yield & high purity synthesis of the [2-] dimer and trimer iron carbonyl from their neutral parents . </li></ul><ul><li>Triiron Dodecacarbonyl </li></ul><ul><li>Diiron nonacarbonyl </li></ul>Strong, H., et.al Inorganic Syntheses 28: 1990. 203–207.
  20. 20. Hierarchy Diiron nonacarbonyl Fe 2 (CO) 9 Triiron Dodecacarbonyl Fe 3 (CO) 12 Iron pentacarbonyl* Diiron dianion [Fe 2 (CO) 8 ] 2- Triiron dianion [Fe 3 (CO) 11 ] 2- New Indium Pyrazolylborate--Iron Carbonyl Complexes “ One Pot” Reaction Indium tris(3,5-dimethyl)-1 Pyrazolylborate
  21. 21. Synthesis of Diiron Nonacarbonyl <ul><li>Photolysis of Commercial Iron Pentacarbonyl </li></ul>2Fe(CO) 5 Fe 2 (CO) 8 + 2 CO hv <ul><li>Temperature Controlled to prevent decomposition </li></ul><ul><li>High Yielding synthesis 90%+ </li></ul>
  22. 23. IR Analysis <ul><li>Carbonyl Peaks are comparable to Commercially available spectra and spectra from literature. </li></ul>
  23. 25. Sigma-Aldrich FT-IR
  24. 26. Synthesis of Triethylenediamine octacarbonylferrate [Fe(C 2 H 4 (NH 2 ) 2 ) 3 ][(Fe 2 (CO) 8 ] <ul><li>Following Heiber, et. al. </li></ul><ul><li>2.5 g of commercial diiron nonacacarbonyl was treated with the molar eq. of ethylenediamine </li></ul>Under nitrogen environment Introduction of ethylenediamine caused a red-sludge like constancy to develop. Release of CO—fog like. Heiber, W., et. al. Chem. Ber. 1957, 90. (2). 278-286. Translated.   Heiber, W., R. Werner.” Chem. Ber. 1957, 90. (2). 286-296. Translated.
  25. 27. Synthesis of Triethylenediamine octacarbonylferrate After rinsing the crystals with water, filtering and drying under vacuum crystals were red/orange in color.
  26. 28. Synthesis of ([Hydrotris[(3,5 dimethylpyrazolyl)borato]indium]octacarbonyldiiron “ One Pot” Reaction + [Fe(C 2 H 4 (NH 2 ) 2 ) 3 ]Cl 2
  27. 30. [Fe(en) 3 ][Fe 2 (CO) 8 ]
  28. 32. 1 HNMR Results <ul><li>NMR spectroscopy of this compound provided an insight as to the structure of this compound. </li></ul><ul><li>Comparing </li></ul>
  29. 35. 1 HNMR (CD 3 SOCD 3 ): δ 5.505, 5.137 (s,s, 2.87, 2.09; 4-H); 3.388, 2.162 (m-m 18.89, 20.39; THF), 2.706, 1.883, (s-s, 45.84, 44.32 Me), 1.507, 0.869, (s-s, Me 15.89, 8.49). The peaks at 5.505 and 5.137 ppm indicate the 4-H position on the Pyrazolyl rings, the peaks at 3.388 and 2.162 provide that a weakly bound THF solvent ligand is attached, keeping the indium octahedral, the peaks at 2.706 and 1.883 show the two equivalent methyl groups on two of the Pyrazolyl rings and the peaks at 1.507 and 0.869 show the nonequivelent methyl groups on the last Pyrazolyl ring. Comparing these 1 HNMR peaks to the ones for the initial Indium tris(3,5-dimethyl)-1 Pyrazolylborate: 1 HNMR (CDCl 3 ): HB[(Me 2 -pz) 3 ]InCl 2 ·THF δ5.97 (1.23, s, 4-Hpz*); 3.80, 1.90 (1.00, 1.90, m, m; THF); 2.60, 2.95 (7.10, 7.10,s,s; 3,5Me-pz*) the peaks have shifted, indicating that the Indium tris(3,5-dimethyl)-1 Pyrazolylborate has coordinated to the diiron complex. The two lone pair of electrons in the reduced state of the ethylenediamine dianion (one from each iron) has donated them to the central indium atom making a new coordination complex.
  30. 38. Synthesis of Triethylenediamine undodecacarbonyl ferrate <ul><li>[Fe(C 2 H 4 (NH 2 ) 2 ) 3 ][(Fe 3 (CO) 11 ] </li></ul><ul><li>Following Heiber, et. al. </li></ul><ul><li>2.5 g of commercial triiron dodecacarbonyl was treated with the molar eq. of ethylenediamine </li></ul>Under nitrogen environment Introduction of ethylenediamine caused a red-sludge like constancy to develop. Release of CO—fog like. Heiber, W., et. al. Chem. Ber. 1957, 90. (2). 278-286. Translated.   Heiber, W., R. Werner.” Chem. Ber. 1957, 90. (2). 286-296. Translated.
  31. 39. Synthesis of Triethylenediamine undodecacarbonyl ferrate After rinsing the crystals with water, filtering and drying under vacuum crystals were red to dark orange in color .
  32. 40. Synthesis of ([Hydrotris[(3,5 dimethylpyrazolyl)borato]indium] undodecacarbonyltriiron “ One Pot” Reaction + [Fe(C 2 H 4 (NH 2 ) 2 ) 3 ]Cl 2
  33. 42. [Fe(en) 3 ][Fe 3 (CO) 11 ]
  34. 43. [HB(Me 2 -pz) 3 ][Fe 3 (CO) 11 ]
  35. 44. Gaussian Molecular Modeling <ul><li>Molecular Modeling Work using Gaussian can be used to predict gas phase IR </li></ul><ul><li>Changing Basis Sets and Level Calculations </li></ul><ul><li>Starting with Hartree-Fock and moving to Møller-Plesset (MP2, MP3, MP4), and progressively to Becke 3-Parameter (B3LYP) </li></ul><ul><li>Starting with Basis Set 6-31,6-311G 6-311G* 6-311G** </li></ul><ul><li>Starting with the tris(3,5-dimethyl) Pyrazolylborate and build structures with increasing complexity </li></ul>
  36. 45. Conclusions <ul><li>Two different ethylenediamine derivatives of iron carbonyl dianions have been synthesized and the synthesis of [Fe 2 (CO) 8 ] 2- was made by adopting the same procedure established by Heiber, et. al. for [Fe 3 (CO) 11 ] 2- . </li></ul><ul><li>These derivatives are much easier to handle and spectra are easily obtainable </li></ul>
  37. 46. <ul><li>Two new iron metal carbonyl complexes have been coordinated to the Indium tris(3,5-dimethyl)-1 Pyrazolylborate Moiety. </li></ul>Conclusions
  38. 47. Further Research <ul><li>Gaussian Modeling to obtain gas phase IR </li></ul><ul><li>X-Ray Crystal Structures </li></ul><ul><li>1 HNMR of [HB(3,5-Me 2 -pz) 3 ]In[Fe 3 (CO) 11 ] </li></ul><ul><li>Transmetalation of Indium tris(3,5-dimethyl)-1 Pyrazolylborate Moiety </li></ul><ul><li>Synthesizing different transition-metal carbonyl dianions to complex to Indium tris(3,5-dimethyl)-1 Pyrazolylborate Moiety </li></ul>Ellis, J. E. Organometallics. 2003,22, 3322-3338.
  39. 48. Acknowledgments <ul><li>Mount Union College </li></ul><ul><li>Department of Chemistry </li></ul><ul><li>Dr. Scott Mason, Dr. Jeffery Draves, & Dr. Debra Boyd-Kimball </li></ul><ul><li>Dr. Mark Himmelein, Mount Union College, Department of Foreign Languages </li></ul><ul><li>Dr. Yan Sun, Case Western Reserve University </li></ul>
  40. 49. References <ul><li>Trofimenko, S. “Boron-Pyrazole Chemistry. II. Poly(1-pyrazolyl)borates” J. Amer. Chem. Soc. 1967, 89 , 3170. </li></ul><ul><li>Reger, Daniel L.; Mason, Scott S.; Reger, Lance B.; Rheingold, Arnold L.; Ostrander, Robert L. “Synthesis and Characterization of Indium(III) Complexes Containing Two Different Chelate Ligands of the Type [Hydrotris(3,5-dimethylpyrazolyl)borate]In[ligand]X”. Inorganic Chemistry, 1994,33, 1811-1816. </li></ul><ul><li>Reger, D.L., Mason, S.S. , Rheingold, A.L., Ostrander, R.L. “Indium (III) Complexes of Potentially Tridentate Poly(pryazolyl)borate Ligands. Ionization of Molecular [HB(pz)3]InCl in CD2Cl2 Solution.” Inorganic Chemistry . 1994, 33 (9). 1803-1810. </li></ul><ul><li>Reger, D.L., Knox, S.J., Rheingold, A.L., Haggerty, B.S. “Indium (III) dihydrobis(pyrazolyl)borate complexes. Crystal and Molecular Structures of {[H2B(pz)2]In(CH3)Cl}2 and [H2B(pz)2]In(CH3)2.” Organometallics. 1990. 9 (9) . 2581-2587. </li></ul><ul><li>Reger, Daniel L.; Mason, Scott S.; Rheingold, Arnold L.; Haggerty, Brian S.; Arnold, Frederick P. “Syntheses and Solid State Structures of [HB(3,5-Me2pz) 3 ]InFe(CO) 4 and [HB(3,5-Me2pz) 3 ]InW(CO) 5 (pz = Pyrazolyl Ring). Intermetallic Complexes with Short Metal-Metal Bonds.” Organometallics. 1994, 13, 5049-5053. </li></ul><ul><li>Collman, J.P. “Disodium Tetracarbonyl Ferrate—a Transition-Metal Analog of a Gringnard Reagent.” Accounts of Chemical Research.” 342-347. </li></ul><ul><li>Strong, H.; Krusic, P. J.; San Filippo, J. (1990). Robert J. Angelici. ed.. &quot;Sodium Carbonyl Ferrate, Na2Fe(CO)], Na2[Fe2(CO)8], and Na2[Fe3(CO)11]. Bis[μ-Nitrido-Bis(triphenylphosphorus)(1+] Undecarcarbonyltriferrate(2-), [(Ph3P)2N]2[Fe3(CO)11 ]&quot;. Inorganic Syntheses 28: 1990. 203–207. </li></ul><ul><li>Heiber, W., et. al. “Über Metallcarbonyle. 79. Mitteil. Neuere Anschauungen Uber Entstehung und Konstitution Äthylendiamin-Haltiger Eisencarbonyle” Chem. Ber. 1957, 90. (2). 278-286. Translated. </li></ul><ul><li>Heiber, W., R. Werner. “Über Vierkernige Carbonyl Ferrate.” Chem. Ber. 1957, 90. (2). 286-296. Translated. </li></ul><ul><li>Ellis, J. E. Metal Carbonyl Anions:  from [Fe(CO) 4 ]; 2- to [Hf(CO) 6 ]; 2- and Beyond. Organometallics. 2003,22, 3322-3338. </li></ul>

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