CHEM 232 Inorganic Chemistry II (Spring 2004)
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Transcript CHEM 232 Inorganic Chemistry II (Spring 2004)
CHEM 232 Inorganic Chemistry II
(Spring 2006)
Instructor: Wa-Hung Leung (ext. 7360, [email protected])
Office: Rm 4528 (Lift 25/26), Lab: Rm 7141
TAs: (1) Zhang Li ([email protected])
(2) Yi Xiaoyi ([email protected])
(3) Wong Wang Yee ([email protected])
(4) Au Yeung Siu Fung ([email protected])
Class schedule:
Lecture: Mon/Wed/Fri, 13:00-13:50 (Rm 2464)
Tutorial/example class (4) : To be confirmed
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Course Contents
1.
2.
3.
Coordination Chemistry
Crystal field theory
Spectral, magnetic, thermochemcial properties
Coordination equilibria, chelate effect
Organometallic chemistry
18 e rule,
Carbonyl, olefin, cycloolefin compounds,
Organometallic reactions, homogeneous catalysis
Main group chemistry
Hydride and alkyl compounds
Element-element multiple bonds
Inorganic rings and cages
Silicates and aluminosilicates
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Assessment scheme
Attendance of lectures and
Quizzes (4)
Assignments (2)
Mid-term exam (~ week 8/9)
Final exam
Tutorials (4) and others
8%
2x4%
38%
40%
6%
• Check out a PRS handset!
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Textbooks and references books
Textbook:
“Inorganic Chemistry” by C. E. Housecroft and A. G. Sharpe,
Prentice Hall (1st ed., 2001; 2nd ed., 2005)
Other suggested readings:
Inorganic Chemistry, 3rd ed., by D. F. Shriver et al., OUP (1999).
Basic Inorganic Chemistry, 3rd ed., by F. A. Cotton et al., Wiley
(1995)
Concepts and Models of Inorganic Chemistry, 3rd ed., by B.
Douglas et al., Wiley (1994)
Inorganic Chemistry, 3rd ed., by G.L. Miessler and D.A. Tarr,
Prentice Hall (2004)
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Websites
Course homepage: http://webct.ust.hk
Useful links
• Department of Chemistry: http://www-chem.ust.hk/
• Textbook website: www.pearsoned.co.uk/housecroft
• Periodic table: For example,
http://www.webelements.com/
http://www.rsc.org/is/viselements.htm
http://pubs.acs.org/cen/80th/elements.html
Conduct in classroom:
http://www.ust.hk/vpaao/conduct/con_classroom_Aug04.ppt
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Coordination Chemistry
• Ref.: Housecroft (Chap. 20), Shriver (Chap. 7)
• Introduction: the metals and ligands
• Crystal field theory: octahedral, tetrahedral, and
square planar geometry
• Spectrochemical series (strong/weak field ligands)
• Electron configurations: LFSE, LS and HS config.
• Spectral, magnetic and thermochemical properties
• Coordination equilibria, chelate effect
• M.O. diagram of ML6
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Coordination compounds (metal complexes)
Metal
n+
L
L
M
L
nX
L
L
L
Counter anion
Ligand
Common geometry
L
L
L
M
L
L
Tetrahedral
L
L
L
M
L
L
Square planar
M
L
L
L
Square pyramidal
L
L
L
L
M
L
L
M
L
L
L
Octahedral
L
L
Trigonal bipyramidal
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The metals
Transition elements (http://www.rsc.org/is/viselements.htm)
Elements with incomplete d shell
(A) Position
First/ second/ third row TMs
Size decreases down a group
Lanthanide contraction (filling of f orbitals)
Sizes of 2nd row and 3rd row TMs are similar
Ion
Size/Å (CN = 6)
Cr3+
0.76
Mo3+
0.83
Ru3+ Ir3+
0.82 0.82
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(B) Early/late TMs
Early: on the LHS of the periodic table (e.g. Ti)
Late: on the RHS of the periodic table (e.g. Pt)
Usually, for metal complexes
Early TM : high metal oxidation state, e.g. Ti(IV), V(V)
(high valent); hard metal ions (binds to hard ligands)
Late TM : low metal oxidation state, e.g. Pt(II), Au(I)
(low valent); soft metal ions (binds to soft ligands)
Why?
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Atomic radius
Ti
Cu
Atomic number
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IE
Ti
Cu
Atomic number
12
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Ligands
(A) Charge (formal charge)
• Neutral (e.g. :CO, :PR3, :NH3)
• Anionic (e.g. Cl-, O2-, CH3-)
• Cationic (rare!) (e.g. NO+, C7H7+)
(B) Hard/Soft properties
Hard : period 1 donor (NH3, OH2)
Soft : carbon (CO, CH3-, CH2=CH2) & period 2 donors
(PR3, SR2)
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(C) No. of donor atom
unidentate
NH3
ammonia
or ammine
N
pyridine
py
bidentate
NH2CH2CH2NH2
ethylenediamine
(en)
N
N
2,2'-bipyridine
bipy
tridentate
NH(CH2NH2)2
diethylenetriamine
(dien)
N
N
N
2,2':6',6"-terpyridine
terpy
Metal complexes with polydentate (chelating) ligands
are more stable than those with unidentate analogues.
Chelate effect
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(ii) p acceptors (p acids)
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Exercises
Classify the following ligands as p donor, p acceptor,
or s ligands
• NMe3
• I• NO+
• CN• OH• H• CH3-
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Nomenclature
(1) Ligands in alphabetical order
(3) Indicate O.N. of metal (in Roman no.: I, II, 0)
(4) Indicate the no. of L and M (di, tri, tetra etc.).
Also bis, tris, tetrakis
(5) Anionic ligand o;
e.g. Cl- (chloro), H- (hydrido), CN- (cyano)
(6) Anionic complexes => ate
e.g. Mn (manganate), Fe (ferrate), Cr (chromate) etc
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(7) Add structural prefixes,
e.g. cis/ trans, fac/ mer etc.
L
L
M
M
L
L
L
M
L
L
M
L
L
L
trans
cis
fac
mer
Examples:
K3[Mn(CN)6]
Tripotassium hexacyanomanganate(III)
Na2[Fe(CO)4]
Disodium tetracarbonylferrate(-II)
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Exercises
Name the following compounds
(1) [Mn2(CO)10], [Co2(CO)8]
(2) [Ru(PPh3)4Cl2]
(3) K2[Pt(CN)4]
(4) [Cr(NH3)3(H2O)(OH)Cl][NO3]
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