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N330 final


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coordination #6
most common for TM (d-0 to d-9) -octahedral
coordination #7
trigonal pentagonal
coordination #8
cubic, dodecahedron
coord number 9
tricapped trigonal prismatic
coordination #4
very common for TM complexes -tetrahedral (early TM -- d-10) - square planar (d-8 complexes)
coodination #5
trigonal bipyramidal (most common when ligands are same) - square pyramidal (common when one ligand is unique)
penetrating power for the 3 emissions
alpha: .03 mm beta: 2 mm gamma: 10cm
in beta decay...
a neutron is converted into a proton and an electron is expelled.
binding energy
the force required to overcome the proton-proton repulsions and allow the nucleus to be stable
all radioactive decays are:
first order b/c, to occur, there needs to be one and only one reactant. The reaction involves only the nucleus of the atom.
acidic oxides
on dissolution in wter, these bind to a water molecule and release a proton (donor)
basic oxides
an oxide to which a proton is transfered (acceptor)
conjugate base
a species with one fewer proton than the parent acid
conjugate acid
a species with one mmore proton than the parent base
are stereoisomers that have diff configurations at one or more chiral centers
6 coord: MA4B2
can form cis and trans (B's)
6 coord: MA3B3
can form meridinal and facial
6 coord: MA2B2C2
all trans, all cis (delta and Lambda (2)), 1 trans and 2 cis (3 of these)
chelate related to stability
- increasing size of chelate increases the stability of the complex - increase in ring size decreases the stability of the complex
3 substitution mechanisms:
associative, dissociative, interchange reaction
associative substitution
incoming base adds before the LG leaves. incoming ligand is very important
dissociative substitution
LG leaves and new ligand adds at the same time. incoming ligand is not that important
trans effect
the effect of a coordinated ligand upon the rate of substitution of ligands opposite to it.
what can inhibit associative mechanism
steric crowding
nitrogenase is an enzyme that contains:
2 proteins: the larger MoFe-protein & the smaller Fe-protein
MoFe protein contains:
part of nitrogenase!! 2 types of a super cluster: P-cluster: which transfers electrons & FeMoco cluster: which is the catalytic site of NH3
part of nitrogenase -> its role is to transfer electrons to the MoFe-protein
hydrogenase physical description:
have fragile active site burried deep in the enzyme, thus necessitating special poors and FeS cluster for long range ET.q
2 types of hydrogenase:
FeFe-hydrogenases &NiFe-hydrogenase
tend to operate in direction of H2 production - found in strictly anaerobic organisms only
catalytically active form assigned as Ni(III)-H(-)
Fe-overload treatment
chelation therapy is used by admistering a ligand to separate Fe from tissues allowing it to be excreted.
Cancer treatments
-cisplatin: designed to stop the growth of cancer cells. This has a lot of neg sideeffects so, carboplatin is also used. - bleomycin: binds to DNA and creates a ferry species that oxygenates sites and leads to degredation.
Anti-Arthritus drugs
-commonly use Au - myochrisin and solganol and auranofin are types
treats arthritus, features Au(I) with linear coordination. cannot be given orally due to hydrolysis in the stomach
helps treat arthritus but cant be given orally due to hydrolysis in the stomach
helps treat arthritus and can be given orally.
complexes that target the heart
complexes that target the brain
complexes that target the kidney
nuclear reactions
AKA transmutations; conversion of an unstable (parent nucleus) to a more stable (daughter) with spontaneous emission of radtiation
smoke detectors
use americium-241 which is absorbed by smoke, which in turn sets off the alarm
blue copper in PC
terminal electron acceptor in photosynthesis
horseradish peroxidase
scavenges free hydrogen peroxide and forms compound I and II reaction: H2O2 + 2e-+2H+ --> 2H2O
Cyt c Oxidase
creates proton gradient across membrane - ET: Cytc --> CuA --> heme a --> binuclear site reaction: O2 + 4e- + 8H+ --> 2H2O +4H+
oxygenases (Cyt P450)
reaction: R-H +O2+ 4e- +2H+ --> ROH + H2O
reductive elimination
reduction of metal by 2e- and release of substrate
using a second metal-alkyl species to deliver the second coupling partner to the active metal center and remove a halide from the catalyst.
trans to cis isomerization
isomerization of the ligands on the metal center which changes the groups to be coupled so they are cis to one another, without this, reductive elimination cant occur
oxidative addition
addition of substrate oxidizes the catalyst by 2e- by adding the R-x substrate to the metal center
peroxidases catalyse reduction of harmful hydrogen peroxide. Also produces Fe(IV) as an intermediate which is vital in numerous biological processes.
enzymes that catalyse the reduction of O2 to water or H2O2 without the incorporation of O atoms into the oxidizable substrate.
catalyse the insertion of one or both O atoms derived from O2 into an organic substrate.
catalyse the insertion of one O atome while the other atom is reduced to to H2O
catalyse the incorporation of both O atoms.
used to cleave an O-O bond. - in one step there will be Fe-O-O with Fe being something other than (IV) then, in the next step it will be Fe(IV)=O
values of L and what they correspond to, and how it relates to n
L=0,1,2,...(n-1) L=1-->p 0-->s 2-->d 3-->f
n= l= ml=
n=which shell l= subshell ml= orbital
effective nuclear charge
explains that since the inner core electrons are btw the outer electrons and the nucleus, they shield the outer electrons (screening effect) from the full positive charge.
EA explained with atomic radii
the smaller the atom, the closer a new electron can get to the nucleus and the stonger the attraction between them.
IE example
an element's change in IE will be moderate until it reaches a noble gas then it will spike quickly bc it doesnt want to lose another electron
cations always have what in relation the their neutral form
cations are always smaller than their neutral form while anions are always bigger
what happens to delta G and Ecell when coefficients are doubled in a rxn
delta G changes but Ecell stays the same (independent of scale)
calculating delta G
calculating standard equilibrium constants
Ecell=RT/nF*ln(K) --> K=e^nFEcell/RT **these are done when conditions are not standard
nernst equation
calculate the cell potential for redox reactions under nonstandard conditions: Ecell=E(o)cell-(RT/nF)lnQ
calculating Ecell with different concentrations
Ecell=E(o)cell-(RT/nF)*log(conc products/conc reactants) **make sure to include coefficients
leveling effect
brings all acids down to the acidity of H3O+ (ex. water)
factors that determine rate of association/dissociation
1. metal centers with high ox numbers will have stronger bonds to ligands than metal centers with low ox numbers 2. steric hinderance will slow down the rate of association.

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