Chem 460 Exam 1 Key

February 5, 2010

1. For each of the following, give the requested data. When assigning point groups, use local symmetry. If the symmetry is ambiguous, give the most symmetric point group possible. **Note: spelling and neatness count! If I cant understand what youve written, its wrong. (12 points each, total of 48) a)
NH3 H2O H2O NH3 Ru NH3 NH3 2+

d electron count on the transition metal is: __d6___

point group is: ___C2v _____

Systematic name (Stock method) is:

cis-tetraammine(diaqua)ruthenium (II)
Systematic name (ACS method) is:

cis-tetraammine(diaqua)ruthenium (2+)

b)
Br NC Cl Cl Cr Br CN 3

d electron count on the transition metal is: __ d3__

point group is: ___ C2v ___

Systematic name (Stock method) is:

cis-dibromo-cis-dichloro-trans(dicyano)chromate (III)

Systematic name (ACS method) is:

cis-dibromo-cis-dichloro-trans(dicyano)chromate (3)

1. (continued) c)
H2 N N H2 F Zr F F F

d electron count on the transition metal is: ___ d0_

point group is: ___ C2v __

Systematic name (Stock method) is:

(ethylenediamine)-tetrafluorozirconium (IV) or (1,2-diaminoethane)-tetrafluorozirconium (IV)

Systematic name (ACS method) is:

(ethylenediamine)-tetrafluorozirconium (0) or (1,2-diaminoethane)-tetrafluorozirconium (0)

d)
NCS Pt H2O SCN P(CH3)3

d electron count on the transition metal is: __ d8__

point group is: ___C2v ___

Systematic name (Stock method) is:

trans-aqua-di(S-thiocyanato)(trimethylphosphine)platinum (II)

Systematic name (ACS method) is:

trans-aqua-di(S-thiocyanato)(trimethylphosphine)platinum (0)

2. Below is the C3v character table. C3v A1 A2 E E 1 1 2 2C3 1 1 1 3v 1 1 0 z Rz (x,y) (Rx,Ry) z2 (x2-y2,xy)(xz,yz)

(a) Prove that the irreducible representations are orthogonal to each other. (6 points)

Orthogonality means Irrep x Irrep = 0 A1 x A2 = (1)(1)(1) + (2)(1)(1) + (3)(1)(1) = 1 + 2 + 3 = 0 A1 x E = (1)(1)(2) + (2)(1)(1) + (3)(1)(0) = 2 + 2 + 0 = 0 A2 x E = (1)(1)(2) + (2)(1)(1) + (3)(1)(0) = 2 + 2 + 0 = 0

(b) Prove that a hypothetical B1 irreducible representation cannot exist for this point group. (10 points)

There is more than one way to solve this. Heres one method. The notation that we use for irreps means that a B1 irrep in C3v symmetry must correspond to characters 1/1/1. In table format, C3v A1 A2 E B1 E 1 1 2 1 2C3 1 1 1 1 3 v 1 1 0 1 z Rz (x,y) (Rx,Ry) z2 (x2-y2,xy)(xz,yz)

A1 x B1 = (1)(1)(1) + (2)(1)(1) + (3)(1)(1) = 1 + 2 + 3 = 2 Since A1 x B1 0, the irreps are not orthogonal, so B1 cannot be an irrep.

(3) For each compound or ion below, use your knowledge of nomenclature to sketch its structure. Use straight lines to indicate bond in the place of the paper, bold triangles to indicate bonds coming out of the paper and squiggles to indicate bonds going into the paper. Make your pictures neat and clear! If I cant understand what youve drawn, its wrong. (6 points each sketch, 12 points total) (a) fac-triammine-tris-(trimethylphosphine)-rhodium(III)

NH3 Me3P Me3P Rh NH3 NH3 PMe3

3+

(b) trans-bis-(2-propanone)-dibromo-palladium(II)

Br Pd O

O Br

3. Circle the compound or ion most consistent with the indicated characteristic. Explain your choice briefly (no more than one or two sentences). (6 points each, total of 24) (a) isoelectronic with ammonia:

C(t-Bu)3

P(C2H5)2

B(i-Pr)3

NH3 has three bonds, one lone pair. This is also true of C(t-Bu3)3. P(C2H5)2 has two bond and two lone pairs, while B(i-Pr)3 has three bonds and zero lone pairs. So only C(t-Bu3)3 is isoelectronic with NH3.

(b) the strongest Lewis acid: Mn2+ Mn3+

Mn4+

Lewis acidity increases as the metal becomes more electron-poor. In other words, Lewis acidity increases with increasing charge on the metal Mn4+ has the largest positive charge of the three, and so is the strongest Lewis acid.

(c) contains a transition metal with a d7 electron count: [Co(CO)4] [Co(NH3)6]3+

CoF42

In the Periodic Table, Co starts as d9. [Co(CO)4] has Co[1], so is d10. [Co(NH3)5]3+ has Co[+3], so is d6. [CoF4]2 has Co[+2], so is d7.

(d) most likely to be a ligand in a transition metal coordination complex ion with CN=8:

CH3CN

CH3S(=O)CH3

(CH3)3N

Fitting 8 ligands around a metal requires that the ligands be small and/or linear. CH3CN has a linear NCC core. DMSO is pyramidal around S, Me3N is pyramidal around N.