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Inorganic Chem > Topic 3 > Flashcards

Topic 3 Flashcards

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1
Q

Arrhenius acid/base

A

acids make protons, bases make OH-

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1
Q

Bronsted-Lowry acid-bases

A

acid is H+ donor, base is H+ acceptor. really only applies to aqueous

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2
Q

Lewis acid/bases

A

acid is e- pair acceptor, base is e- pair donor

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3
Q

MO Explanation of Lewis acids and base interactions

A

frontier orbitals (HOMO and LUMO) proximity in energy. this can also tell us which part of the molecule will interact

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4
Q

bond diagram

A

like MO diagram but for hybridization of acid and base

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5
Q

adduct

A

thing from the bond formed

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6
Q

coordinate covalent bond

A

less strong than covalent

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7
Q

how to see if an adduct is formed

A

change in boiling point compared to reactants (higher - stronger bonding)

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8
Q

oxidation occurs..

A

e- want to go from HOMO to a lower LUMO and if they can jump they will leave leading to that spp being oxidized

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9
Q

charge-transfer band

A

appears on UV vis. exchange of 4 or more eV is in UV range but fewer appears in visual range

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10
Q

Pearson’s theory

A

hard and hard acids and bases, soft and soft acids and bases

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11
Q

hard and soft A/B

A

based on electron cloud mobility. Hard is very compact and dense charge, soft is large and spread out charge.

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12
Q

hard acid examples

A

H+, Li+, K+, Na+, Be2+, Mg2+, Ca+, BF3, BCl3, B(OR)3, Al3+, AlCl3, Al(CH3)3, Sc2+, Ti2+, Cr2+, Mn2+, (L side of table)

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13
Q

soft acid examples

A

Cu+, Ag+, Au+, Pd+, Pt2+, Cd2+, Hg2+, Tl+, Pb2+ (R side of table)

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14
Q

borderline acid examples

A

Fe2+, Co2+, Ni2+, Cu2+, Zn2+, Ru3+, Rh3+, Os3+, Ir3+, B(CH3)3 (large AND highly charged)

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15
Q

hard bases examples

A

F-. Cl-, O2-, OH-, H2O, ROH, RO-, NH3, RNH2, N2H4, NO3-, CO3(2-), SO4(2-), PO4(2-) = p-block top

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16
Q

soft bases examples

A

I-, H-, CN-, CO, benzene, ethylene, S2- and everything under O, SCN-, SH-, SR-, PR3 (phosphine), P(OR)3, AsR3

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17
Q

Eq constant and favorability

A

K>1 is favorable, K<1 is unfavorable

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18
Q

borderline bases examples

A

Br-, pyridines, N///N

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19
Q

solubility of compounds

A

based on bond strength

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20
Q

hard HOMO/LUMO

A

hard has low (close to Nu) homo, large gap to LUMO. bases have higher energy than acids. better ionic bonding

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21
Q

soft HOMO/LUMO

A

higher energy and smaller homo-lumo gap. bases again higher E than acids. better covalent bonding

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22
Q

HOMO energy is similar to

A

ionization nrg

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23
Q

LUMO energy is similar to

A

electron affinity

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24
absolute hardness
(ionization energy - e- affinity)/2
25
dative bond
bond btwn M and L (aka coordination covalent)
26
main coordination compound apps
pharmaceuticals, catalysts, dye
27
Jorgenson chain theory
guy didnt know how coordination works, thought everything was like organic molecules. POINT AND LAUGH
28
Alfred Werner
figures out octahedron and coordination, father of inorganic chem
29
naming coordination compounds rules
complex goes in brackets. ligand names first, in alpha order. -o for negative ligands, add charge of metal, metal in -ate if it is an anionic complex, cis/trans for isomers, use mu for bridging ligands
30
chelating agents
multidentate ligands (strong grasp)
31
example bidentate ligands
ethylene diamine (en). bipyridine (bipy), 1,2-bis(diphenylphosphine) ethane (dppe), acac-
32
tridentate..multidentate examples
diethylenetriamine... triethylenetetramine (keep adding chains
33
hexadentate ligand example
ethylenediamine-triacetate (EDTA)
34
stereoisomers
changes where things are bonded but not what they bond to. like in coordination sphere. can be chiral or like arrangement of diff things in octahedron
35
constitutional isomers
changes where ligands are bonded. ex. hydrate isomers where water enters/leaves coordination sphere or ionization where metal charge changes and ligands are displaced for counterions in the coordination sphere
36
coordination isomers
multiple coordination spheres together exchange ligands but M:L within spheres is constant
37
linkage isomer
switches the ligand atom to which the center is bound
38
coordination numbers
help us determine shape (= how many sites is it bound to a ligand at). also = number of lone pairs donated
39
CN = 1
only works for an insanely bulky ligand
40
CN 2 and 3
can occur with d=10 metals.
41
CN 4`
most commonly square planar (Pt)
42
CN5
trigonal bipyramidal, (these are same in soln) square pyramidal, pentagonal planar
43
CN 6
most common, octahedral. sometimes can be trigonal prism due to linear ligand
44
CN 7
pentagonal bipyramidal, capped trigonal prism, capped octahedral
45
CN 8+
capping (adding more ligands) to existing shape ie octahedral
46
order of color changes with inc bond strength
green>yellow (red to purple absorption)
47
crystal field theory
repulsion splits metal d-orbitals. 2 higher energy orbitals can interact with ligands (destabilising). This repulsion can be larger or smaller to change the size of the gap. does not explain strong/weak ligands.
48
ligand field theory
MO theory + crystal field. basically build MOs and splitting due to symmetry causes nb to be much lower than antibonding and gap changes based on ligand orbital position (strength)
49
ligand types
sigma donor (gives e-, destabilizes metal), pi donor (gives pi, destabilizes metal), pi acceptor (accepts pi e- into pi star, destabilizes ligand - strong)
50
sigma donor ligand examples
H2O, NH3, en
51
pi donor ligand examples
I, Br, Cl, OH-, O2CR, F-
52
pi acceptor ligand examples
NO2, CN, CO
53
when is there a nb metal orbital
when only sigma bonds from L are present
54
weak vs strong ligands
weak have smaller delta o, strong have larger delta o
55
how is splitting modified by ligand type
pi acceptors have much higher energy (closer to d orbitals) so the character of the antibonding is close to them and the M gets the bonding orbitals, so distance btwn metal character is larger. for pi/sigma donors, the ligand e- go to stabilized orbitals leaving M with antibonding (close to its og position)
56
high vs low spin complexes
high spin is weak (small deltaE) bc the e- can move freely btwn orbitals. low spin is strong bc e- cannot spread out btwn the large distance btwn orbitals
57
order of ligand strength (by type)
pi donors, sigms donors, pi acceptors
58
metal impacts on delta o
higher charge and lower position (2nd and 3rd row) - diffuse charge both allow larger splitting
59
hapticity
of atoms thru which a ligand can bond, shown by long n^x power.
60
denticity
can be symbolized by k^n (kappa) for how many atoms (non-contiguous) it can use to bond with M
61
ionic model of e- counting
move all e- in bond onto L, note its charge, count those e- plus those remaining for M.
62
x-type ligands
anionic
63
l-type ligands
neutral
64
18 e- rule
like octet rule
65
angular overlap method
there are charts for ligand type (sigma donor, pi donor/acceptor), which can be used to construct MO diagram. charts use strongest sigma/pi interaction as "reference energy" and splitting is based on units of that. input ligands based on position, add up rows for their energy, add up columns of the ligands used for the d orbital energies (leads to their splitting). This can be mapped out. know which ligand type to determine stabilization or destabilization of that magnitude.
66
orbital splitting for octahedron
t2g and eg* splitting. t2g is nb for sigma, bonding for pi*, antibonding for pi
67
value of e(pi) for pi acceptors
negative
68
charge and splitting magnitude
more charge leads to more splitting (also depends on ligand interaction strength) (high spin is more favored if orbitals can be singly occupied)
69
splitting in td vs oh
td has smaller splitting bc orbitals interact less with the ligands, literally spatially much further and orbitals are side-to-side
70
e(x) and ligand size
typically larger size means longer bond, smaller splitting
71
electronegativity and splitting
more electroneg leads to more strong bonding, larger splitting
72
Janh-Teller theorem
degenerate orbitals cannot be unevenly occupied (they stop being degenerate and symmetry changes if this is allowed)
73
elongation and compression
J-T splitting, cause orbitals so split and change symmetry due to change in point group
74
why do some metals like square planar
distortion from J-T splitting
75
chirality symbols
clockwise it delta, counterclockwise its upside down v
76
cis/trans for octahedron
fac/mer (same face or on axis)
77
diamagnetic
all e- are paired
78
paramagnetc
upaired e-, higher spin
79
enantiomers
when mirror image is non superimposable
80
hard stuff...
H- is SOFT. more charge usually = harder.
81
finding the crystal field splitting
draw the salcs overlap for the shape, see which have most proximity (higher energy/lower for pi*)
82
angular overlap remember..
energy units are in + or -, e(pi) is 1/5-1/10th of e(sigma)
83
MO diagram letter order of orbital energy levels for metal
lowest to highest: d, s, p.
84
MO reminders
energy comparison of d orbitals= just use angular overlap first
85
angular overlap for pi and sigma
subtract the energies for both for metal d orbitals
86
mixing more than 3 orbitals
mix 1/2 L orbitals with 1/2 M orbitals so it is multiple sets of paired orbitals. make these pairings based on the best match btwn M orbital and SALC, keep in mind that p is u and d is g.
87
ligands with tricky names
NCS (binds with N = isothiocyanate. binds with S = thiocyanate). NO2- = nitrito, CS = thiocarbonyl, CH3NC = methylisocyanidea
88
what does the direction of the chirality mean
which direction does it REFLECT LIGHT
89
electron counting for NO
bent = it goes -, linear = it goes +
90
charge determination by adding
if less than 18, -, if more than 18 +
91
if no e- count for m is given..
assume 18 e!!

Inorganic Chem (4 decks)

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