CHEM 528 (061)

Inorganic and Organometallic Reaction

Mechanism
Major Exam
NAME

ID #

1. Anation of [Cr(NH3)5(H2O)]3+ is thought to proceed by an

increasing mechanism. The table below presents rate constants
and activation parameters for interchange of the entering and
leaving groups in the Cr coordination sphere at 50oC.
_______________________________________________________________
Entering ligand

104 k(s-1)

H (kJ/mol)

S (J/Mol K)

_______________________________________________________________
NCS-

6.12

102

12

HC2O-4

6.2

112

39

C2O2-4

6.2

104

33

H3PO4

1.45

H2PO4-

1.45

[Co(CN)6]3-

2.5

103

26

H2O (exchange)

13.7

97

_______________________________________________________________

What do these data suggest about the intimate mechanism of

these reactions?

(ex 11.1)

2. Some volumes of activation for base hydrolysis are given

below. Rationalize the trends observed.
______________________________________________________
Complex
V (cm3/mol
______________________________________________________
[Co(NH3)5(O = C(NMe2)H]3+
+43.2
+32.7
[Co(NH2Me)5Cl]2+
2+
[Co(NH2Et)5Cl]
+31.1
trans-[Co(en2)Cl2]+
+24.8
+
cis-[Co(en2)Cl2]
+27.9
_________________________________________________________

(Ex 1.2)

2. Exchange of NH3 in [Pt(NH3)4]2+ has recently been studied. The reaction

[Pt(NH3)4]2+ +

15

NH3

[Pt(15NH3)(NH3)3]2+ + NH3

was followed in buffered aqueous solutions having 0.050 < [NH3]

< 0.50. The rate law was found to be
rate = (k1 + k2[15NH3])[Pt(NH3)4]2+ .
k1 = 3.9 x 10-10 s-1 and k2 = 9.5 x 10-10 M-1 s-1.
(a) What do these data suggest about the exchange mechanism?
(b) Calculate the half-life for ammonia exchange in 1.0 M NH3.
(c) [Au(NH3)4]3+ was found to undergo similar exchange with
15

NH3; the rate law is of the same form with k1 = 3 x 10-6 s-1 and k2

= 1.69 x 10-1 M-1 s-1. What can you say about the mechanism of
exchange for AuIII?

(Ex 1.3)

3, Account for the difference in rate constant for the following two
reactions:
[Fe(H2O)6]2+ + Cl- [FeCl(H2O)5]+ + H2O

k = 106 M-1 s-1

[Ru(H2O)6]2+ + Cl- [RuCl(H2O)5]+ + H2O

k = 10-2 M-1 s-1

(p 11.2)

4. The reactions [Cr(NCS)6]3- + solv [Cr(NCS)5(solv)]2- + NCShave been investigated and found to have the following rate constants near
70oC.
_______________________________________________
Solvent
k (s-1)
___________________________________________
Dimethylacetamide
9.5 x 10-5
Dimethylformamide
12.4 x 10-5
Dimethylsulfoxide
6.2 x 10-5
_______________________________________________
What do these values suggest about the intimate mechanism of these
reactions?

(P 11.7)

5. The following activation parameters have been measured for the reactions
[PtClL2X] + py [PtCiL2py]+ + Xin methanol at 30oC.
------------------------------------------------------------------------------------------------------------------------Complex
K2 x 103 (M-1 S-1) H (kJ/mol) S (J/mol K)
V (cm3/mol)
trans-[Pt(NO2)py2Cl]
7.35
49.3
-94
-8.8
cis-[Pt(NO2))py2Cl]
0.150
55.2
-110
-19.8
trans-[Pt(PEt3)2Cl2
0.53
53.9
-100
-13.6

What mechanistic information can be extracted from these values?

( P 11.21)

6. Activation volumes for acid hydrolysis of cis-[PtCl2(NH3)2] and [PtCl2en] are

-9.5 (at 45oC) and -9.2 (at 41oC) cm3/mol, respectively. How are these values
consistent with what you know about the mechanism for square-planar
substitution?

(P 11.22)

7. The following rate constants (in M-1 s-1) were measured for reduction of Co
complexes:
----------------------------------------------------------------------------------------------------

[Ru(NH3)6]2+

Complex

[Ru(NH3)5(H2O)]2+

----------------------------------------------------------------------------------------------------

[Co(N3)(CN)5]3[Co(NCS)(CN)5]3-

1.71
0.81

2.06
099

----------------------------------------------------------------------------------------------------

Comment on the inner or outer-sphere mechanism of these four reactions

(P 11.28)

8. The presence of excess L = PMe2Ph catalyze the isomerization

of cis-[Pt(Cl)2L2] to trans-[Pt(Cl)2L2]. Suggest a mechanism for
this reaction

(P 11.34)