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CHEM 3111/6170 Second test

Topics, metal chemistry, coordination compounds, electronic spectroscopy of transition metal compounds October 29th, 2003 50 minutes to complete Maximum score 76 points 1) Classify all of the following ligands according to their bonding modality as some combination of donor, acceptor and donor. (6 points) Phenanthroline NH3 H2O BrCO CH32) donor and acceptor donor donor and donor donor and donor donor and acceptor donor

Rank the following groups of ligands according to their ability to produce large values of . Put the ligand giving the largest first. No partial credit. (4 points) a) b) phen, H2O, ClCO, NH3, Iphen > H2O > ClCO > NH3 > I-

3)

Very briefly explain why most octahedral coordination complexes of Co(III) are diamagnetic, but CoF63- is paramagnetic. (4 points) Most octahedral cobalt complexes are low spin and hence diamagnetic. CoF63- is paramagnetic as it is high spin. The metal is high spin because the fluoride ligands produce a very small value ( donors) and B is quite high because the complex is not very covalent.

Name: 4) Very few Ti(II) compounds have been synthesized and studied using optical spectroscopy. However, dissolution of TiCl2 in molten aluminum chloride is thought to give rise to species similar to octahedral TiCl64-. The optical spectrum of this melt shows the presence of two absorption bands at 1 = 7600 cm-1 and 2 = 14,500 cm-1. a) Using one of the attached Tanabe-Sugano diagrams assign these spectroscopic transitions. ( 4 points) 1 3T2g <- 3T1g 2 3T1g <- 3T1g b) Estimate values for and B' for TiCl64- (6 points) 1/2 ~ 1.91. This corresponds to /B ~ 16.7 For 2 E/B ~ 28.0 if /B ~ 16.7. This gives B = 518 cm-1 and = 8648 cm-1 c) B for gas phase free Ti2+ is 718 cm-1. Explain why the free ion value is different from the one you have just determined. (2 points) B for the complex is lower than for the free ion as in the complex the electrons are partially delocalized onto the ligands and this reduces the amount of electron electron repulsion.

5)

For each of the following colored compound indicate the primary mechanism that is responsible for the color of the compound. Your options are A) spin forbidden d-d transition, B) d-d transition, C) Ligand to metal charge transfer, D) Metal to ligand charge transfer and E) charge transfer between metals in different oxidation states. Pale pink aqueous Mn2+ (2 points) Intensely purple MnO4- solutions. (2 points) Prussian blue ( Fe4[Fe(CN)6]3.xH2O ) (2 points) Yellow orange [Co(en)3]3+ (2 points) Yellow-orange CrO4- (2 points) Blue CoCl42- (2 points) A C E B C B 2

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6)

NiCl42- is paramagnetic, Ni(CN)42- is diamagnetic and BPh4- (Ph= pheyl) is also diamagnetic. Using general chemical principles plus the observed magnetic properties, deduce the shapes of these three species. (6 points) NiCl42Ni(CN)42BPh4Tetrahedral Square planar Tetrahedral

7)

Draw all the possible isomers for a complex of the type Co(en)X2Y2. Indicate which ones are enantiomers. (8 points) Cl Co Cl Cl Co NH3 + NH3 NH3 + Cl NH3 NH3 + Cl Co Cl NH3 Cl Co NH3 + NH3 Cl

N N

N N

N N

N N

The last two are related as enantiomers (they are chiral) 8) For each of the following groups identify one ion that is most likely to form a Jahn-Teller distorted six coordinate complex with the ligand NH3. (6 points) a) Cu2+, Co3+, Cr3+, Ti4+ b) Ca2+, Zn2+, Mn2+, Mn3+ c) Fe3+, Co3+, Cr2+, Cr3+ 9) Sodium dissolves in dry liquid ammonia to give a blue solution. Write a balanced equation showing the reaction that gives rise to the blue colored product. (2 points) Na(s) -(Am liq)--> Na+(am) + e-(am)

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10)

Using your general knowledge of the factors that lead to metal-metal bonding in transition metal compounds deduce which one of the compounds in each of the following groups is metal-metal bonded. (4 points) a) CrCl2, MoCl2, TiCl2 b) NbO, FeO, MgO

11)

For each of the following complexes calculate the ligand field stabilization energy. In order to do this you may have to determine if the species is high or low spin. (12 points) a) [Mn(OH2)6]2+ b) [Co(NH3)6]3+ c) [Fe(CN)6]3+ t2g3eg2 LFSE = 0 t2g6eg0 LFSE = 6 * 2/5 = 12/5 o t2g5eg0 LFSE = 5 * 2/5 = 2 o

d) Tetrahedral [FeCl4]2- e3t23 LFSE = (3*3/5t - 3*2/5t) = 3/5 t

Name: d2 Tanabe Sugano diagram

Name: d3 Tanabe Sugano diagram

Name: d4 Tanabe Sugano diagram

Name: d5 Tanabe Sugano diagram

Name: d6 Tanabe Sugano diagram

Name: d7 Tanabe Sugano diagram

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Name: d8 Tanabe Sugano diagram

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