Chapter 23. Transition Metals and Coordination Chemistry
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1 Chapter 23 Transition Metals and Coordination Chemistry
2 The Transition Metals: Exact Definition Transition metal: An element whose atom has an incomplete d subshell or which can give rise to cations with an incomplete d subshell. (official IUPAC definition)
3 The Transition Metals: Exact Definition What about Zn, Cd, and Hg? Officially, they are NOT transition metals (often called noble metals) Unofficially, they usually grouped with transition metals because of similarities in chemistry and because they are completing the d-orbital filling.
4 Electronic Configuration of d-block metals
5 Where Found? - Minerals Most metals, including transition metals, are found in solid inorganic compounds known as minerals. Minerals are named by common, not chemical, names.
6 Properties of Transition Metals What s so special about transition metals atoms and ions have partially filled d subshells low energy, unoccupied d orbitals Results ions of variable oxidation state (i.e. Fe 2+ and Fe 3+ ) magnetic properties Form complex ions (act as Lewis acids) many make good catalysts (i.e. Pt, Pd, Rh in catalytic converter) ion orbital energy differences = visible photon energy (colored) Ti 3+ Cr 3+ Mn 2+ Fe 3+ Co 2+ Ni 2+ Cu 2+
7 Properties of First-Row TM
8 Atomic Radii Left to right across a row, the radius of TM decrease then increase. Increasing effective nuclear charge tends to make atoms smaller. However, the strongest (and shortest) metallic bonds are found in the center of TM. Move further to right filling anti-bonding orbitals so bonds weaken.
9 Atomic Radii Mn: radius inc. likely due to electron going into ½-filled 4s subshell and Mn still fairly small more repulsion Periods 5 and 6 size about same. period 6 lanthanide contraction adding protons to nucleus & filling 4f orbitals which don t shield well - inc. effective nuclear chg. - offsets expected inc. in size due to adding electrons as go down group - similar chemical prop.
10 Electron Config. & Oxidation States For a given TM the (n-1)d orbitals smaller than ns and np orbitals (wave fncs drop off more rapidly than ns and np) - d-electrons can behave like valence electrons or like core electrons - depends on location in PT and atom s environment
11 TM charges and oxidation states TM lose outer s-electrons before d-electrons Fe : [Ar]3d 6 4s 2 Cu : [Ar]3d 10 4s 1 Fe 2+ : [Ar]3d 6 Cu + : [Ar]3d 10 Fe 3+ : [Ar]3d 5 Cu 2+ : [Ar]3d 9
12 Ex: What are the electron config. for Co 2+ and Co 3+? Ex: What is the electron config. for Cr 3+?
13 Because most TM have partially occupied d subshells, the metals and/or their cmpds often: - Have more than one oxidation state - colored - exhibit magnetic properties
14 Oxidation States
15 Most common: +2 - due to loss of 4s e Next most common: +3 - Sc (grp 3B) always +3 - noble gas config. (Sc 3+ is [Ar]) Max. ox. st. inc from +3 to +7 from Sc to Mn then dec. beyond Mn - d electrons become more core like - Zn always +2 (can t remove d e )
16 Higher ox. st. - No isolated ions > +4 (e.g. in soln.) - inc. covalent character most common oxidation state for Ti is +4, but the Ti 4+ ion not found as an isolated ion - bonding is highly covalent Ti [Ar]4s 2 3d 2 TiO 2 Ti ox. # = +4
17 Mn highest oxidation state is +7, - only found in MnO 4 Periods 5 & 6 : ox. st. as high as +8 - larger 4d & 5d orb Max. ox. st. only when metal combined w. most electroneg. elements O, F, sometimes Cl
18 VO 3+ VO 2+ V 3+ V 2+ Ox. St Color yellow blue blue-grn violet
19 Magnetism Electron possesses spin - has magnetic moment (behaves like a tiny magnet) Diamagnetic all e paired - magnetic moments cancel - non magnetic - actually very weakly repelled by magnet
20 Paramagnetic Results from an atom having unpaired electrons. Not influenced by e on adjacent atoms or ions Magnetic moments randomly oriented In magnetic field mag. mom. align parallel to each other Net attraction to mag. field
21 Ferromagnetic Unpaired e influence each other to align in the same direction Exhibit strong attractions to an external mag. field Permanent magnets. Fe, Co, Ni, alloys (CrO 3, Fe 2 O 4 )
22 Antiferromagnetism Unpaired e on adjacent atoms align in opposing directions. These magnetic fields tend to cancel each other. Cr, FeMn alloys, Fe 2 O 3, LaFeO 3, MnO
23 Ferrimagnetic Spins align opposite each other, but the spins are not equal NET magnetic field Prop. similar to ferromag. materials Examples are NiMnO 3, Y 3 Fe 5 O 12, and Fe 3 O 4.
24 Ferromag, Ferrimag & Antiferromag become paramag. at temp. above a critical temp. - spins become random - Curie Temp., T C, ferromag & ferrimag - Néel Temp., T N, antiferromag
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