Академический Документы
Профессиональный Документы
Культура Документы
1. Draw the molecular orbitals for the cyclic π-system of benzene. Assuming that one benzene is
bound to a given metal facially (along the z axis) determine which metal orbital (if any) will interact
the best with each molecular orbital drawn.
2. For the following complexes, draw the most likely geometry, indicate the coordination
environment at Ni, give the d electron count and the number of unpaired electrons:
a) [Ni(en)3]2+; b) [NiCl4]2-; c) [Ni(CN)4]2-.
3. On the basis of the 18 electron rule, identify the first-row transition metal for each of the
following:
a) [M(CO)7]+; b) H3CM(CO)5; c) M(CO)2(CS)(PPh3)Br; d) [(η3-C3H5)(η3-C5H5)M(CO)]-; e)
(OC)5M=C(OCH3)(C6H5); f) [(η4-C4H4)(η5-C5H5)M]+; g) [M(CO)4I(dppe)]- (dppe = 1,2-
bis(diphenylphosphino)ethane).
4. Determine the metal-metal bond order consistent with an 18-electron count for the following:
a) [(η5-Cp)Fe(CO)2]2; b) [(η5-Cp)Mo(CO)2]22-
5. On the basis of the 18-electron rule, determine the expected charge on the following:
a) [Co(CO)3]z; b) [Ru(CO)4(CMe3)]z; c) (η3-C3H5)V(CNCH3)5]z; d) [(η5-Cp)Fe(CO)3]z.
6. Select the best choice in each of the following and briefly justify the reason for your selection.
a) Shortest C-O bond:
Ni(CO)4 [Co(CO)4]- [Fe(CO) 4]2-
b) Highest C-O stretching frequency:
Ni(CO)3(PH3) Ni(CO)3(PF3) Ni(CO)3(PCl3) Ni(CO)3(PMe3)
c) Best π acceptor ligand:
NO- O2 O2- O22-
8. An unusual bonding mode of the carbonyl ligand has been reported by R. D. Adams et al. in J.
Am. Chem. Soc. 1992, 114, 4918, in which the carbon bridges two metals while oxygen is bonded to
a third. Would you predict that the carbonyl stretching frequency in this bridging mode would be
higher or lower than for ordinary doubly bridging CO ligands? Explain briefly.