CHEM 3030.04 2014 STYNES 408 CB MWF 12:30 CLH M (F) [email protected] TUTORIALS 8:30 am M or W in CLH- J TEXT : HS = Housecroft and Sharpe or 3 rd Ed 2007 or 4 th 2012 or SA= Shriver and Atkins etc (5 th Ed) 2010 or CWG= Cotton, Wilkinson, and Gaus, Basic Inorganic Chemistry 3 rd Ed. 1995 . Other General Inorganic Texts- Douglas. MacDaniel and Alexander (DMA) / Purcell and Kotz / Huheey (H)/ Miessler & Tarr (MT)

SOFTWARE FOR STRUCTURE VIEWING Free Mercury graphic package from Cambridge http://www.ccdc.cam.ac.uk/products/csd_system/mercury/

GRADING quizzes 40% or 30%*, Assignments 30%, Final 30% or 40%* * If final exam grade is higher than the lowest quiz

COURSE OUTLINE - All handouts, problem sets and old exams are found on the course website http://www.yorku.ca/stynes/inorg

1. Introduction to Coordination Chemistry. Coordination Numbers, geometries, common HS 19 , CWG 6, 24,25, SA 7 or H -12 { browse HS 23 & 24 for descriptive chemistry}

2. Valence Bond, crystal field, and MO theory of octahedral, tetrahedral, and square planar complexes, d-d and CT spectra. HS 20, CWG 23 SA 20 DMA 10 or H-11 . A1, A2, A3, A6.

3. Introduction to X-ray Crystallography and space groups A5, A7 . posted notes , slides 1 and 2, Expt 5. Space group s Tutorial http://people.brandeis.edu/~foxman1/teaching/indexpr.html http://img.chem.ucl.ac.uk/sgp/large/sgp.htm 4. Mechanisms of Inorganic Reactions HS 26, CWG 6.5, SA 21 , A4 / DMA 11 / H-13 substitution and transfer reactions, Marcus theory , e-transfer proteins

5. Organometallics and π- acid ligands HS 24, CWG 28,29, SA22 DMA 12, 13 / H-15 /

6. Organometallic reactions & catalysis by metal complexes HS 25, CWG30, SA26, DMA 14, H-15.

More Advanced or Specialized works (A# below) 1. Cotton & Wilkinson 3rd through 6 th Edition : special topics in Part 4. 2. Lever, Inorganic Electronic Spectroscopy 1 st Ed. - d-d spectra 3. Schlafer & Gliemann or Figgis - 4 Basolo and Pearson - Mechanisms of Inorganic Reactions 5. Sands- Intro. to Crystallography / Stout & Jensen- X-ray Structural Determination 6. Gray and DeKock- Chemical Structure & Bonding 7. Atkins- Physical Chemistry – Chapter 23 in 7 th Ed on crystallography 8. A list of Primary Journal references downloadable at pubs.acs.org is posted on 3030 website. There will be weekly problem sets 1-3 and 4-9 which will be covered in tutorials.

Learning Objectives . Pre-requisite Chemistry Skills – Full use is made of basic concepts and skills taught in first and second year chemistry courses. Students will be responsible for reviewing these concepts as required. The philosophy “use them or lose them” applies to these skills. Concepts and skills include: drawing molecular structures, drawing Lewis structures, resonance, symmetry and point groups, fundamentals of valence bond and theory, inorganic and organic nomenclature, elementary thermodynamics, G,H, S, and E o, rate laws, kinetics and mechanisms, applications of NMR and IR spectroscopy. These concepts will be widely used in the course and expanded upon in specific applications to transition metal chemistry. Students are encouraged to make use of the primary literature easily accessed via pubs.acs.org or sci-finder or google search engines.

Crystallography . Students are taught the basics of X-ray diffraction, space groups and structure solution. Students use the Hg software (free download from Cambridge CCDC) to visualize structures and view results in cif files available from the primary literature. Crystallographic data is commonly presented in studies of inorganic, organic, and biochemical molecules. This course prepares students to access it online and to make intelligent use of it. 1. Apply symmetry operations to a point (x,y,z) including screw axes, mirrors, glide planes, rotation, inversion. 2. Generate the full space group tables for simple cases such as Pm, P-1, P2 1, Cm, etc. 3. Using space group tables: obtain coordinates of symmetry equivalents, identify systematic absences, note constraints in special positions. For high symmetry cases such as Fm3m, Z =4 identify the location of all atoms and compute structure factors. 4. Describe the 14 Bravais lattices. 5. Solve a structure using the SHELX software starting from diffraction data supplied. 6. Define difference map, Fourier series for e-density, phases, R factor. 7. Compute d spacing, Bragg angles, and density for a given crystal.

Coordination Chemistry 1. Describe the basic geometries for coordination numbers 2-9 and give an example of each. 2. Apply valence bond, crystal field, and MO theory to octahedral, square planar and tetrahedral transition metal complexes. Obtain crystal field stabilization energies. 3. Predict the spin only magnetic moments of complexes. Use the Gouy and Evans method to obtain experimental magnetic moments. 4. Derive Term symbols. Recognize high and low spin states. Know trends in the parameter 10Dq and explain them. 5. Analyze weak field spin allowed d-d spectra of complexes d 1 through d 9. Obtain 10Dq and B from spectral data. Give examples of MLCT and LMCT charge transfer transitions. 6. Use Tanabe Sugano diagrams to analyze d-d spectra for strong field cases and spin forbidden transitions. 7. Describe geometric and optical isomers of octahedral, square planar, and tetrahedral complexes. Distinguish between symmetric, dissymmetric and asymmetric complexes. 8. Describe a laboratory synthesis of a cobalt (III), chromium (III), and Ni(II) complex. 9. Apply the Jahn Teller theorem. 10. Give examples of stereochemical nonrigidity and the application of NMR to them. 11. Describe the Nobel prize work of Werner, Taube, Marcus, Grubbs, Ziegler, Sharpless, Perutz, etc. 12. Trace major advances and trends in research in inorganic from 1900 to present day. 13. Give a synopsis of the chemistry of a common t-metal Ti V Cr Mn Fe Co Ni Cu including classical complexes, organometallics, spectra, rates and mechanisms of reactions.

Mechanisms. 1. Order the common metal ions in terms of lability and explain trends. 2. Describe the basic mechanisms of substitution of octahedral Co(III) and square planar Pt(II) complexes. Give examples of pH dependent rate laws and interpret rate laws. 3. Discuss steric and electronic effects in substitution reactions. 4. Describe inner and outer sphere mechanisms for electron transfer. 5. Cite specific evidence supporting specific mechanisms. (rate laws, stereochem, steric and electronic effects, istotope labeling etc.) 6. Describe the factors in the Marcus theory for adiabatic outer sphere electron transfer. 7. Estimate cross reaction rates from redox potential data and self-exchange rate constants.

Organometallics and Catalysis . 1. Apply the 18 and 16 NVE rule to organometallics. Use the hapto nomenclature. 2. Describe the carbonyls and of Ti through Ni, their synthesis and some reactions. 3. Interpret CO stretching frequencies in terms of pi bonding. 4. Explain the sigma/pi backbonding descriptions of carbonyl ,olefin, and cyclopentadienyl complexes of metals. 5. Draw stereochemically accurate structures of a variety of organometallic complexes. 6. Describe five or six basic reaction types for organometallic complexes and apply these to catalytic sequences. 7. Describe complexes containing CO, NO,CS, N 2, H 2, hydride, Phosphines, halides, alkyls, olefins, dienes, allyls, cyclooctatetraene, cyclopentadiene, carbenes etc and their properties. 8. Describe some important known catalysts and the evidence pertaining to their proposed mechanisms: Wilkinson’s catalyst, Wacker process, hydroformylation, isomerization, chiral catalysts, Ziegler Natta polymerization, Grubbs catalyst.