Transcript Slide 1
A Very Brief Introduction to Boron Chemistry Kristina Orosz Nov. 5, 2004 Uses of Boron • Borosilicate glasspyrex • Detergents • Flame retardants • Ceramics • Pyrotechnics • Used in production of impact resistant steels • Control rods in nuclear reactors Common Bonds in Boranes • • • • 2c-2e3c-2e2c-2e3c-2e- B-H B-H-B B-B B-B-B Diborane B2H6 Huheey, J. E.; Keiter, E. A.; Keiter, R. L. Inorganic Chemistry: principles of structure and reactivity, 4th ed. New York: HarperCollins College Publisher, 1993. 790. B2H6 MO Diagram Wade, K. Electron Deficient Compounds. London: Nelson, 1971. 30. Tetraborane B4H10 Huheey, J. E.; Keiter, E. A.; Keiter, R. L. Inorganic Chemistry: principles of structure and reactivity, 4th ed. New York: HarperCollins College Publisher, 1993. 794. Dodecaborane [B12H12]2- Huheey, J. E.; Keiter, E. A.; Keiter, R. L. Inorganic Chemistry: principles of structure and reactivity, 4th ed. New York: HarperCollins College Publisher, 1993. 795. Elemental Forms of Boron a- rhombohdral b-rhombohedral, B12(B12)12, (B12)(B12)(B60) Housecroft, C. E.; Sharpe, A. G. inorganic Chemistry. New York: Pearson Education Limited, 2001. 251-2. Boron Deltahedra – Parent Clusters Housecroft, C. E.; Sharpe, A. G. inorganic Chemistry. New York: Pearson Education Limited, 2001. 275. Boron Hydrides Housecroft, C. E.; Sharpe, A. G. inorganic Chemistry. New York: Pearson Education Limited, 2001. 272. Huheey, J. E.; Keiter, E. A.; Keiter, R. L. Inorganic Chemistry: principles of structure and reactivity, 4th ed. New York: HarperCollins College Publishing, 1993. 799. Wade’s Rules • n = number of B atoms in parent closodeltahedron • Always n+1 bonding e- pairs and n+1 bonding MOs – nido has n-1 vertices – arachno has n-2 vertices – hypho has n-3 vertices Using Wade’s Rules • Find total available bonding e-s: – Each B-H unit gives 2 e-s – Each additional H gives 1 e– Overall charge • Find parent closo-deltahedron – n+1 bonding e- pairs – Is it closo, nido, arachno, hypho? – Lose highest connectivity B first then lose adjacent sites • Determine number of remaining hydrogen atoms – Each vertex has a H – “sew up” hole with H atoms • Bridging H atoms • Low connectivity B atoms can get another 2c-2e- B-H bond • Try to keep it as symmetrical as possible Huheey, J. E.; Keiter, E. A.; Keiter, R. L. Inorganic Chemistry: principles of structure and reactivity, 4th ed. New York: HarperCollins College Publisher, 1993. 798. Carboranes C2B10H12 ortho meta or neo para Huheey, J. E.; Keiter, E. A.; Keiter, R. L. Inorganic Chemistry: principles of structure and reactivity, 4th ed. New York: HarperCollins College Publisher, 1993. 801. Boron Neutron Capture Therapy (BNCT) • • • • • 10B has large cross-section for neutron capture 10B + a + 7Li Products can kill cells Cancer treatment Cages - need high [10B] in cell References Dreiss, Matthias, ed., and Heinrich Nöth, ed. Molecular Clusters of the Main Group Elements. Weinheim: Wiley-VCH, 2004. 95-125. Housecroft, Catherine E. Boranes and Metallaboranes: structure, bonding, and reactivity. 2nd ed. New York: Ellis Horwood, 1994. 1-20, 93-116. Housecroft, Catherine E., and Alan G. Sharpe. Inorganic Chemistry. New York: Pearson Education Limited, 2001. 245-279. Huheey, James E., Ellen A. Keiter, and Richard L. Keiter. Inorganic Chemistry: principles of structure and reactivity. New York: HarperCollins College Publishers, 1993. 789-801. Wade, Kenneth. Electron Deficient Compounds. London: Nelson, 1971. 1-61.