Inorganic Final

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Author:
Anonymous
ID:
189221
Filename:
Inorganic Final
Updated:
2012-12-12 23:33:25
Tags:
inorganic chemistry
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Inorganic final
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  1. WF ----> SF
    I− < Br− < S2− < SCN− < Cl− < NO3− < N3− < F− < OH− < C2O42− < H2O < NCS− < CH3CN < py  < NH3 < en < bipy < phen < NO2− < PPh3 < CN− < CO
  2. Trends in liability of metal complexes
    • d e-    WF(high spin)     SF(Low Spin)
    • 1            Liable                   Liable
    • 2            Liable                  Liable
    • 3            Inert                     Inert
    • 4              Liable                 Inert
    • 5            Liable                    Inert
    • 6            Liable                  Inert
    • 7              Liable                 Inert
    • 8                intermediate       (sq. planar) inert
    • 9              Liable                Liable
    • 10             Liable               Liable
  3. Liable Vs  Inert
    • Liable
    •   - low Ea
    •   - thermodynamically stable
    •   - Filling eg weakens M-L bonds, b/c they are antibonding,
    •   - t1/2 < 1 minute, Taube

    • Inert 
    •   - high Ea
    •   - t2g^3-6  and  eg^ 0
    •         - eg electrons weaken M-L bonds & promote subst.
    •         - t2g doesn't affect bonding and makes L' approach unfavorable b/c of e/e repulsion
    •   - crystalized more easily than labile
    •    
  4. Pt2+, Pd2+, Ir+, Au3+ geometry w/ SF ligands 
    • Square planar
    •   - dx2-y2 is empty & points directly at ligands
    •  - z2 no ligands there (doesn't matter if electrons are there)
  5. Lability & period, oxidation state
    • 3d > 4d > 5d
    •   - 3d smaller therefore more polarizable --> less electrostatic interxns, hard bond to break - also better orbital overlap

    • high oxidation
    •  - less labile, electrons more tightly held so more Erequired to dissocate 

    • low oxidation
    •  - more likely to occupy eg orbitals, easier M-L bond discc. 
  6. Experimental Kinetics
    determine Ea and Sa --> study rxn at diff T

    • activation volume
    • - D generally result in +values for Vactivation, because one species splits into two

    A result in - Vactivation values, because two species combine into one, with a presumed volume smaller than the total for the reactants

    Caution because solvation effects, particularly for highly ox. cations, may be larger than the difference expected for the reaction otherwise

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