030.

442 - Organometallic Chemistry - Karlin

Problem Set 1 - Spring 2009

Name_________________

1. For each of the following diamagnetic compounds indicate the coordination number, oxidation state, d-electron configuration and coordination geometry about the central transitionmetal. Coordination # a) FeBr(CO)5 b) Rh(!-C5H5)(C2H4)2 c) [Pt(SnCl3)5]3d) (COT)Fe(CO3)
COT = cyclooctatetraene

Oxidation State Fe(I)

dn d6

Geometry Octahedral

e) Mo(!-C5H5)(CO)3H f) Pd(bipy)(C3H7)2 g) (R3P)AuMe3 h) [Co(!-C5H5)2]+BF4i) Mn(CO)(NO)3 j) Pt(PEt3)2(Me)2I2 2. Assign the charge z (which may also be zero) to each of the following diamagnetic complexes. a) [Mn(CNR)6]z (b) [Ni(dpe)(CF3)(I)]z (c) [OsL3(CO)(H)(Cl)]z 31 (exhibits two P nmr signals) e) [Rh(Me2PCH2CH2PMe2)2(O2)]z

d) [Co(CN)4((!-C5H5)(C3H5)]z

3. Which of the two complexes has the lower energy CO stretching frequency in the infrared spectrum? Rationalize your choice a) [W(CO)5Cl] or Re(CO)5Cl

b)

Mo(CO)4(PMe3)2 or Mo(CO)4(PPh3)2

030.442 - Organometallic Chemistry - Karlin Problem Set 1 - Spring 2009 (page 2, continued) 4.

Name_______________

Identify the central element in each of the following diamagnetic complexes a) b) c) d) M(NO)3CO (1st row element) M(PF3)4 (3rd row element)

[M(dpe)2(H)(Cl)] (2nd row element) [(!-Cp)2M]+ (3rd row element)

5.

Propose a logical structure for the following polynuclear (i.e. more that 1 metal) structures. a) b) c) d) e) Pt2(Me)4(COT) WMo(!-Cp)2(CO)6 Mn2CO10 [Me3Pt(I)]4
(Note: halides can doubly or even triply bridge metal ions)

[(!-Cp)(CO)2Mo]2

(consider mulitple Mo-Mo bonding)

6.

Predict the product of reaction: a) b) c) d) (CH3)Mn(CO)5 + PPh3 (Cl)Rh(PPh3)3 Ni metal + Re2O7 + + H2

"" ""
(show likely geometry)

xs CO " "

xs CO " " Pt(NH3)2Cl2.

7.

(a) Write out all the possible isomers of

(b) What are the ligand hapticities (i.e., denticities) in [Cr(CpCH2CH2Cp)(CO)2] ? Draw a three-dimensional formula.