| Terms |
Definitions |
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PPh₃
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Triphenylphosphate
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Ethylene
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C₂H₄
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C5H5N
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pyradine
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Boric Oxide
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B₂O₃
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inert element
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neon
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Aluminosilicates
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Clays, talc, mica
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anion
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negatively charged ion
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CO32-
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carbonate -> carbonato
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Use of UV-vis
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Electronic spectroscopy
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Nitrito
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NO₂ bound through O
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Quantum l
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Angular momentum (0,1,2,n-1)
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Δ₀ > P
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Low-spin, strong field
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Linkage isomers
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Occur with ambidentate ligands
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Hydrochloric Acid
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HCL - Acid pH=2
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electronegativity
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the attraction for shared electrons
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n
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Number of atoms in the molecule
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Transition state of SN2
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7 coordinate
Pentagonal bipyramidal
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BX₃
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Electron deficient
Often act as lewis acids
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Ligands
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Attached to the metal
Don't readily dissociate in water
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pH of 1.0 M strong base
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pH=14
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Solute
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The dissolved substance in a solution
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Trialkyl boranes are pyrophoric/polyphoric?
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Trialkyl boranes are pyrophoric.
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Number of vibrations for a non-linear molecule
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3n-6
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Elemental B
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Extremely hard, high melting point, low chemical reactivity
Interlinked icosahedral units (B₁₂ units) in the shape of a closed cage
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LCAO approximation
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For a particular wavefunction, the estimate (expectation value) of the orbital energy (E - previously
referred to as ε ) is given by :
∫
∫ =
ψ ψ τ
ψ ψ τ
d
H d
E
.
ˆ .
*
*
[2]
where:
ψ - molecular orbital wavefunction (expressed as LCAO)
ψ* - complex conjugate of ψ (ψ* = ψ if the wavefunction is entirely real).
Ĥ - effective one-electron Hamiltonian
dτ - integral over all space
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Dissociative mechanism
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Common for octahedral complexes. 1) leaving group falls off, 2) 5-coord intermediate forms, 3) entering group bonds to metal
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Two coordinate Mg complexes require what to be stable?
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Bulky R groups
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Reason tetrahedral complexes are always high-spin
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Δt = 4/9 Δ₀
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crystal field
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consists of charged ligands; can split energy of d orbitals by electric field
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coordination number
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number of its closest neighbors within the lattice (1-6)
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Beta-hydrogen abstraction
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Hydrogen in beta position of alkyl ligand is removed by the metal center, resulting in coordinated alkene.
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equal
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in molecules of only one element, the electronegativity is
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Oxidation of the metal involves transfer of one electron to the aromatic system producing..? a paramagnetic radical anion
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a paramagnetic radical anion
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Uses of boric oxide
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Borosilicate glass
Very low thermal expansion coefficient
Pyrex or Kimax
Cooking, laboratory glassware, lenses for telescopes
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alkali metal physical properties
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soft, silvery-white; mp and bp decrease down group; form ionic cmpds;
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Cone angle
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Measure of ligand size, where line is drawn from metal to edges of ligand. Important for catalysis because ligand size affects reactivity of metal center. Removal of large cone angle species alleviates steric strain, stabilizing the transition state and increasing reaction rate.
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Reasons poryphyrins are used in PDT
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Good cell penetration
Long wavelength absorption
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Environmental issues of Al production
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Red mud (highly basic)
HF gas
Oxides of C
Fluorocarbons
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surface tension
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a measure of how difficult it is to break surface of liquid
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Molar absorptivities of octahedral TM complexes
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≤ 150 M⁻¹cm⁻¹
Because Δl = 0
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Difference between octahedral and square planar
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Square planar only has 4 ligands, therefore they are held tighter and the electron repulsion is higher
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Cp2Ca,Cp2Sr, and Cp2Ba are insoluble/soluble in ether and hydrocarbon solvents?
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Cp2Ca , Cp2Sr and Cp2Ba are insoluble in ethers and hydrocarbons solvents.
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Crystal Field Stabilization Energies (CSFE)
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Energy in actual field - energy in spherical field
Stabilizing force
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In most compounds, the group 14 element is tetravalent/trivalent.
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In most compounds, the group 14 element is tetravalent.
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Several general properties of group 14 (E) organo-dervatives are:
The E-C bonds are generally of low/high polarity?
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The E-C bonds are generally of low polarity
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Carbonyl
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CO
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C5H4N-C5H4N
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dipyridyl
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u
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Ungerade (odd)
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Cisplatin
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[Pt(NH₃)₂Cl₂]
d⁸ square planar
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BN
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Isoelectronic with C-C
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cation
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positively charged ion
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ε
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Molar absorptivity coeficient (M⁻¹cm⁻¹)
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2B + 3X₂ ➝
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2BX₃
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Lewis acid/base
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e- pair acceptor/donor
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cohesion
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related do surface tension
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Use of IR
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Vibrational spectroscopy
Identifies types of bonds present
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Corundum
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Type of anhydrous aluminum oxide
Rubies, sapphires
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7
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neutral on ph scale (water)
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Na[Cp] is pyrophoric but its air-sensitivity can be lessened by complexing the Na with _____.
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dme
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Aliphatic
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C is sp3 hybridized (single bond)
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Low energy waves
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Low frequency, long wavelength
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Photodynamic therapy
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Photogeneration of cisplatin analogs from octahedral Pt(IV) precursors
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Metal character of Al
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Mainly metallic
Amphoteric oxides
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Chelates
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multidentate ligands that form more than one bond; many form 5-6 membered rings
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alpha particle (α)
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mass 4, charge 2
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ion
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atom/ molecule with electrical charge resulting from gain/loss of electrons
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IC₅₀
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Concentration required to kill 50% of cells
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Absorption max
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Wavelength needed to promote electron from t2g to eg
CF bands or d-d bands
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Counter ions
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Offset the charge of the complex
Readily dissociate in water
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Actinides
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radioactive element w/ Z>82; up to Z=94 are naturally occuring, others are formed in nuclear reactors
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Solution
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A mixture of Solids, liquids, and gases without clear boundaries.
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Dinuclear Pt complexes
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Binds DNA at 2 well-separated positions
Increased cytotoxity
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Polarizing effect is more pronounced with...
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Larger sized anions
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buffer
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must contain conjugate pair of a weak acid and weak base; minimize change in pH
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ionization energy
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amount of energy required to remove one electron from each atom ionization energy increases as it moves across the periodic table and decreases as it goes down the periodic group requires less energy to remove an outer electron shell versus an inner electron shell
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Oxidative addition
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Rxn that increases coord # and oxidation state of metal by 2 and adds 1 or 2 ligands.
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very stable/ unreactive
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atoms that fill outermost energy levels are
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Anation
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pH ≤ 7
Replacement of a bound water by an anion
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Octahedral orbital energies
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eg: x²-y², z² (3/5 Δ₀ more unstable)
t2g: xy, xz, yz (2/5 Δ₀ more stable)
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expanded shells
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3rd and higher period can make more than 4 bonds
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chemical compound
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2 or more different atoms in definite proportions
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For octahedral complexes, TM ions with __, __, __, and __ d electrons, the number of unpaired electrons is dependent on Δ₀
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4, 5, 6, 7
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Group 3 bonds have...
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More covalent character due to the larger charge/size ratio
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Arrance the given series of triaryl derivatives in decreasing order: R3Bi , R3As, R3Sb
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R3As > R3Sb > R3Bi
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Differences in laboratory synthesis of ONO and NO₂ isomers
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ONO uses concentrated ammonia, NO₂ uses 2M ammonia
ONO must be cooled in an ice bath, NO₂ remains at room temperature
ONO must be at a pH of 7, NO₂ must be at a pH of 4
ONO adds an additional 3mL of 6M HCl, NO₂ adds 15mL of concentrated HCl
ONO requires a cold water rinse, while NO₂ does not
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π backbonding (pi donation)
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e- from d-orbital of metal are donated to a π* anti-bonding orbital on another atom or ligand
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Effect of bond strength on stretching frequencies
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As bond strength increases, stretching frequency increases
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Atomic radii trend for group 3
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Due to inefficient e⁻ shielding, Ga, In, and Tl atomic radii are smaller than expected (about equal to Al)
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Binding sites for cisplatin
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N-7 (N not bound to the ribose ring in the 5-m ring) of G and A
Guanine is favored
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Reason many 2nd and 3rd row TM complexes are colorless
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Δ is higher; therefore, the energy needed to promote an electron is out of the visible range
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