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CHEM 232 Inorganic Chemistry II (Spring 2006)

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CHEM 232 Inorganic Chemistry II (Spring 2006). Instructor : Wa-Hung Leung (ext. 7360, chleung@ust.hk ) Office: Rm 4528 (Lift 25/26), Lab: Rm 7141 TAs : (1) Zhang Li ( chzhl@ust.hk ) (2) Yi Xiaoyi ( xyyi@ust.hk ) (3) Wong Wang Yee ( chyee@ust.hk )

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CHEM 232 Inorganic Chemistry II (Spring 2006)
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  1. CHEM 232 Inorganic Chemistry II (Spring 2006) • Instructor: Wa-Hung Leung (ext. 7360, chleung@ust.hk) Office: Rm 4528 (Lift 25/26), Lab: Rm 7141 • TAs: (1) Zhang Li (chzhl@ust.hk) (2) Yi Xiaoyi (xyyi@ust.hk) (3) Wong Wang Yee (chyee@ust.hk) (4) Au Yeung Siu Fung (alexwill@ust.hk) • Class schedule: Lecture: Mon/Wed/Fri, 13:00-13:50 (Rm 2464) Tutorial/example class (4) : To be confirmed

  2. Course Contents • Coordination Chemistry Crystal field theory Spectral, magnetic, thermochemcial properties Coordination equilibria, chelate effect 2.Organometallic chemistry 18 e rule, Carbonyl, olefin, cycloolefin compounds, Organometallic reactions, homogeneous catalysis 3. Main group chemistry Hydride and alkyl compounds Element-element multiple bonds Inorganic rings and cages Silicates and aluminosilicates

  3. Assessment scheme Attendance of lectures and • Quizzes (4) 8% • Assignments (2) 2x4% • Mid-term exam (~ week 8/9) 38% • Final exam 40% • Tutorials (4) and others 6% • Check out a PRS handset!

  4. Textbooks and references books Textbook: • “Inorganic Chemistry” by C. E. Housecroft and A. G. Sharpe, Prentice Hall (1st ed., 2001; 2nd ed., 2005) Other suggested readings: • Inorganic Chemistry, 3rd ed., by D. F. Shriver et al., OUP (1999). • Basic Inorganic Chemistry, 3rd ed., by F. A. Cotton et al., Wiley (1995) • Concepts and Models of Inorganic Chemistry, 3rd ed., by B. Douglas et al., Wiley (1994) • Inorganic Chemistry, 3rd ed., by G.L. Miessler and D.A. Tarr, Prentice Hall (2004)

  5. Websites • Course homepage: http://webct.ust.hk • Useful links • Department of Chemistry: http://www-chem.ust.hk/ • Textbook website: www.pearsoned.co.uk/housecroft • Periodic table: For example, http://www.webelements.com/ http://www.rsc.org/is/viselements.htm http://pubs.acs.org/cen/80th/elements.html • Conduct in classroom: http://www.ust.hk/vpaao/conduct/con_classroom_Aug04.ppt

  6. Coordination Chemistry • Ref.: Housecroft (Chap. 20), Shriver (Chap. 7) • Introduction: the metals and ligands • Crystal field theory: octahedral, tetrahedral, and square planar geometry • Spectrochemical series (strong/weak field ligands) • Electron configurations: LFSE, LS and HS config. • Spectral, magnetic and thermochemical properties • Coordination equilibria, chelate effect • M.O. diagram of ML6

  7. Coordination compounds (metal complexes) Common geometry

  8. The metals Transition elements (http://www.rsc.org/is/viselements.htm) • Elements with incomplete d shell (A) Position First/ second/ third row TMs • Sizedecreasesdown a group • Lanthanide contraction (filling of f orbitals) Sizes of 2nd row and 3rd row TMs are similar Ion Cr3+ Mo3+ Ru3+ Ir3+ Size/Å (CN = 6) 0.76 0.83 0.820.82

  9. (B) Early/late TMs Early: on the LHS of the periodic table (e.g. Ti) Late: on the RHS of the periodic table (e.g. Pt) Usually, for metal complexes • Early TM : high metal oxidation state, e.g. Ti(IV), V(V) (high valent); hard metal ions (binds to hard ligands) • Late TM : low metal oxidation state, e.g. Pt(II), Au(I) (low valent); soft metal ions (binds to soft ligands) • Why?

  10. Atomic radius Ti Cu Atomic number

  11. IE Ti Cu Atomic number

  12. Ligands (A) Charge (formal charge) • Neutral (e.g. :CO, :PR3, :NH3) • Anionic (e.g. Cl-, O2-, CH3-) • Cationic (rare!) (e.g. NO+, C7H7+) (B) Hard/Soft properties Hard : period 1 donor (NH3, OH2) Soft : carbon (CO, CH3-, CH2=CH2) & period 2 donors (PR3, SR2)

  13. (C) No. of donor atom Metal complexes with polydentate (chelating) ligands are more stable than those with unidentate analogues. Chelate effect

  14. (ii) p acceptors (p acids)

  15. Exercises • Classify the following ligands as p donor, p acceptor, or s ligands • NMe3 • I- • NO+ • CN- • OH- • H- • CH3-

  16. Nomenclature (1) Ligands in alphabetical order (3) Indicate O.N. of metal (in Roman no.: I, II, 0) (4) Indicate the no. of L and M (di, tri, tetra etc.). Also bis, tris, tetrakis (5) Anionic ligand o; e.g. Cl- (chloro), H- (hydrido), CN- (cyano) (6) Anionic complexes => ate e.g. Mn (manganate), Fe (ferrate), Cr (chromate) etc

  17. (7) Add structural prefixes, e.g. cis/ trans, fac/ meretc. Examples: K3[Mn(CN)6] Tripotassium hexacyanomanganate(III) Na2[Fe(CO)4] Disodium tetracarbonylferrate(-II)

  18. Exercises • Name the following compounds • (1) [Mn2(CO)10], [Co2(CO)8] • (2) [Ru(PPh3)4Cl2] • (3) K2[Pt(CN)4] • (4) [Cr(NH3)3(H2O)(OH)Cl][NO3]