1. Iron Carbonyl Dianions Stabilized by the Indium tris(3,5-dimethyl)-1 Pyrazolylborate Moiety Brandon Alexander Chemistry Seminar

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

7. Adding the Metal Center Synthesis L=tris ligand, [HB(Me 2 -pz) 3 ] Reger, et. al. Organometallics . 1994. -1

12. -2 Naphthalene Na (s) + Synthesizing the Metal Carbonyls into a [2-] Dianion -CO

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

25. Sigma-Aldrich FT-IR

27. Synthesis of Triethylenediamine octacarbonylferrate After rinsing the crystals with water, filtering and drying under vacuum crystals were red/orange in color.

28. Synthesis of ([Hydrotris[(3,5 dimethylpyrazolyl)borato]indium]octacarbonyldiiron “ One Pot” Reaction + [Fe(C 2 H 4 (NH 2 ) 2 ) 3 ]Cl 2

30. [Fe(en) 3 ][Fe 2 (CO) 8 ]

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.

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 .

40. Synthesis of ([Hydrotris[(3,5 dimethylpyrazolyl)borato]indium] undodecacarbonyltriiron “ One Pot” Reaction + [Fe(C 2 H 4 (NH 2 ) 2 ) 3 ]Cl 2

42. [Fe(en) 3 ][Fe 3 (CO) 11 ]

43. [HB(Me 2 -pz) 3 ][Fe 3 (CO) 11 ]