Transition metals and rxn's of aq ions Flashcards
ligand
molecule/ion w l.p of e- that forms co-ordinate bonds w metals (lewis base = e- lp donor)
complex
central metal atom/ion w co-ordinately bonded ligands
monodentate NH3 substitution rxn w hexaqua Co2+ ion eqn
CON
[Co(H₂O)6]²+ + 6NH3 –> [Co(NH3)6]²+ + 6H₂O
no change in CON (6) neutral ligands
monodentate NH3 substitution rxn w hexaqua Cu2+ ion eqn
CON
colour change
incomplete substitution
[Cu(H₂O)6]²+ (aq) + 4NH3 (aq) –> [Cu(NH3)4(H₂O)2]²+ (aq) + 4H₂O (l)
from blue sol to deep blue sol
no change in CON (6) neutral ligands
monodentate Cl- substition rxn w hexaqua Cu2+ eqn
CON
colour change
shape change
[Cu(H₂O)6]²+ + 4Cl- –> [CuCl4]²- + 6H₂O
blue sol to yellow sol
CON changes from 6 to 4 as Cl- are larger and only 4 can bond to metal ion
octahedral to tetrahedral
monodentate Cl- substition rxn w hexaqua Co2+ eqn
CON
shape change
[Co(H₂O)6]²+ + 4Cl- –> [CoCl4]²- + 6H₂O
CON changes from 6 to 4 as Cl- are larger and only 4 can bond to metal ion
octahedral to tetrahedral
monodentate Cl- substition rxn w hexaqua Fe3+ eqn
CON
colour change
shape change
[Fe(H₂O)6]3+ + 4Cl- –> [FeCl4]- + 6H₂O
violet sol to yellow sol
CON changes from 6 to 4 as Cl- are larger and only 4 can bond to metal ion
octahedral to tetrahedral
monodentate Cl- substition rxn w hexaqua Al3+ eqn
CON
colour change
shape change
[Al(H₂O)6]3+ + 4Cl- –> [AlCl4]- + 6H₂O
colourless sol to colourless sol
CON changes from 6 to 4 as Cl- are larger and only 4 can bond to metal ion
octahedral to tetrahedral
bidentate ligand substitution rxn w ethane-1,2-diamine and hexaqua Cu eqn
CON
[Cu(H₂O)6]²+ + 3NH₂CH₂CH₂NH₂ –> [Cu(NH₂CH₂CH₂NH₂)3]²+ + 6H₂O
no change in CON as there’s 3 ligands and each forms 2 coordinate bonds so 3x2=6
bidentate ligand substitution rxn w ethanedioate and hexaqua Cu eqn
CON
[Cu(H₂O)6]2+ + 3C₂O4²- –> [Cu(C₂O4)3]4- + 6H₂O
no change in CON as there’s 3 ligands and each forms 2 coordinate bonds so 3x2=6
multidentate ligand substitution rxn w EDTA4- and hexaqua Cu eqn
charge?
[Cu(H₂O)6]²+ + EDTA4- –> [Cu(EDTA)]²- + 6H2O
2+ + 4- = -2 charge change
small ligands (H₂O and NH3) complex shape, CON, angles, isomerism and give an eg
octahedral shape
CON 6
90 adjacent ligands, 180 opp
CisTrans isomerism eg. [CrCl₂(H₂O)4]+
bidentate ligands isomerism
optical isomerism
pair of enantomers - arrangement of 2 coordinate bonds for each ligand resulting in non superimposable mirror images
chelate effect
eg.
enthalpy change is aprox 0 why?
how does the rxn occur?
substitution of monodentate w bi/multidentate ligand results in more stable complex
eg. [Cu(NH3)4(H2O)2]2+ + 2 NH2CH2CH2NH2 –> [Cu(NH2CH2CH2NH2)2(H2O)2]
2+ + 4NH3
Cu–N bonds formed have similar enthalpy
same number of bonds broken and made
entropy change is positive. 3 to 5 molecules, disorder inc bc more
particles formed
free-energy change is -ve
Larger ligand Cl- shape, CON, angle
tetrahedral 109.5
CON 4
Pt²+ and Ni+ complexes shapes, CON, angle, isomerism
square planar 90
CON 4
CisTrans isomers - eg. Cisplatin and Transplatin
Ag+ complexes shape, CON, angle
Linear
CON 2
180
eg. [Ag(NH3)₂]+ in tollens reagent
vanadium Oxidation state +5 colour
VO₂+
yellow solution (you)
vanadium Oxidation state +4 colour
VO²+
blue solution (better)
vanadium Oxidation state + 3 colour
V 3+
green solution (get)
vanadium Oxidation state +2 colour
V²+
violet solution (vanadium)
effect of ligands on redox potential
standard electrode potentials measured in aq sol –> ions surrounded by water ligands.
other ligands make RP larger/smaller depends on how well they bind to metal ion
effect of pH on redox potential
easier to oxidise in alkaline conditions
easer to reduce in acidic conditions
reduction of [Ag(NH3)₂]+ to metallic silver half eqn
[Ag(NH3)₂]+ + e- –> Ag + 2NH3