OUTLINE

General properties of metal complexes and ligands

Basic definitions

Inner sphere vs outer sphere of coordination

Electronegativity

Formal oxidation state and dn configuration

Hard vs soft acids and bases, small vs large atoms and ions

Structure of ligands : Lewis structures, VSEPR

Hapticity

Denticity

Spectator vs actor ligands, innocent vs non-innocent ligands



Coordination chemistry: Structure

Coordination number and geometry

Nuclearity

Isomerism

Nomenclature





 Werner’s complexes - Isolation

Alfred  Werner  
1866  -­‐  1919  

CoCl3  .  6NH3  orange-­‐yellow    Luteo  

CoCl3  .  5NH3  purple      Purpureo  
CoCl3  .  4NH3  green      Praseo  
CoCl3  .  4NH3  violet      Violeo    
CoCl3  .  3NH3  green      Praseo  
   

… COMPLEXES!

http://www.nobelprize.org/nobel_prizes/chemistry/laureates/1913/#
Werner’s complexes

Reactivity and coordination number

Experimental  observaEons:  
 
CoCl3  .  6NH3  +  xs  AgNO3  give 3  AgCl(s)    
 
CoCl3  .  5NH3  +  xs  AgNO3  give   2  AgCl(s)    
 
CoCl3  .  4NH3  +  xs  AgNO3  give  1  AgCl(s)  
 
CoCl3  .  3NH3  +  xs  AgNO3  give  no  reacEon  
       
Werner’s  conclusion:  
There  are  two  types  of  chloride  ions  (coordinated  and  uncoordinated)  
and  a  constant  coordina9on  number  of  6  
 
[Co(NH3)6]Cl3            +    3AgNO3  →      [Co(NH3)6][NO3]3    +    3AgCl    
 
[Co(NH3)5Cl]Cl2    +  2AgNO3  →      [Co(NH3)5Cl][NO3]2    +    2AgCl    
 
[Co(NH3)4Cl2]Cl    +  AgNO3    →      [Co(NH3)4Cl2]NO3    +    AgCl    
 
[Co(NH3)3Cl3]          +  AgNO3    →      no  reacEon
Werner’s complexes - Isolation

Alfred  Werner  
1866  -­‐  1919  

CoCl3  .  6NH3  orange-­‐yellow    Luteo  

CoCl3  .  5NH3  purple      Purpureo  
CoCl3  .  4NH3  green      Praseo  
CoCl3  .  4NH3  violet      Violeo    
CoCl3  .  3NH3  green      Praseo  
   

[Co(NH3)6]Cl3  
 
[Co(NH3)5Cl]Cl2  
 
[Co(NH3)4Cl2]Cl      
 
[Co(NH3)4Cl2]Cl       … COMPLEXES!

 
[Co(NH3)3Cl3]    
Werner’s complexes

Isomer counting and geometry assignment

Werner’s complexes

Isomer counting and geometry assignment

MA4B2

planar

trigonal

prismatic

octahedral

Only  the  octahedral  spa9al  arrangement  accounts  for  the  presence  of  two  
isomers  for  CoCl3  .  4NH3        
Werner’s complexes

Isomer counting and geometry assignment

Only  the  octahedral  spa9al  arrangement  accounts  for  the  presence  of  two  
isomers  for  CoCl3  .  4NH3        

Note: There is a NEGATIVE EVIDENCE argument in Werner’s conclusion!

Werner’s complexes

CoCl3  .  6NH3    orange-­‐yellow    Luteo  
CoCl3  .  5NH3    purple      Purpureo  
 
 
CoCl3  .  4NH3    green      Praseo  
CoCl3  .  4NH3    violet      Violeo      

cis  
violeo trans  
praseo
COORDINATION COMPOUNDS
coordination number (CN) the number of ligand bonds to the central metal or
the number of central metal coordination sites
occupied

Available range of CN for transition metals: 1 - 12

factors that govern coordination numbers include:

size and charge of the central metal

(large radii, high oxidation states favor higher CN)

steric interactions of the ligands

(bulky, charged ligands favor lower CN)

electronic interactions between central metal and ligands

(geometry and d configuration are linked to type of ligand bonding)
COORDINATION CHEMISTRY OF THE d-BLOCK ELEMENTS
ligands arrange themselves in the lowest energy structure, but there are additional factors
besides electron pair repulsion that govern the shape of coordination compounds

valence shell electron pair repulsion is often NOT the primary determinant of shape for
coordination compounds, with a few exceptions:

d0 Ti4+, Sc3+,Y3+, Zr4+, …

d5 high spin Mn2+ and Fe3+
d10 Ni0, Pd0, Cu+, Ag+, Zn2+, Cd2+, …
COORDINATION NUMBERS AND STRUCTURES
CN 1 gas phase NaCl

CN 2 linear 180°

L–M–L [H3N – Ag – NH3]+ Ag(NH3)2+ HgCl2

rare CN – d10 metals

CN 3 trigonal planar 120°

L SR2 Cu(SR2)3
R 2S Cu Pt(PPh3)3
SR2
M
L L

rare CN – bulky ligands and/or d10 metals

CN  4    square  planar    90,  180°      D4h              
     
    L                       L                    
                   
Cl Cl 2- PtCl42-­‐  
 
                  Pt
 
M  Ni(CN)42-­‐  
Cl Cl
  L L
 
     
 
   tetrahedral        109.5°    Td  
 
                                 
  L Cl -
  CrO42-­‐  
     
  Fe CoCl42-­‐  
  M Cl  
  L Cl
L Cl
  L
 
 
 
 intermediate  or  distorted  structures  exist,  and  interconversion    
 through  a  D4h                    Td  equilibrium  process  can  occur    
COORDINATION NUMBER 4
tetrahedral complexes are favored by small metal centers and/or large/charged ligands
COORDINATION NUMBER 4
Square planar complexes are favored by d8 configuration and, in the case of 1st row TM,
by small ligands  
 
 
CN 5 trigonal bipyramidal 90, 120, 180°
(TBP)
Fe(CO)5
L Ni(CN)53-

L
L M
L
L

square pyramidal 90, 180°

(SP)
Ni(CN)53-
L

L L
M
L L

both structures of [Ni(CN)5]3- exist in the [Cr(en)3][Ni(CN)5] unit cell

CN 5 TBP interconversion    
 
pseudorota9on  (Berry  rearrangement)  through  a  SP  intermediate  
leads  to  TBP  interconversion,  due  to  the  small  energy  difference  
between  the  structural  extremes  
 
   
 
  A1 A1 E1
 
E1
    E1 A1
E M E M M
  3     3 E3
  E2 A2
E2
    A2
A2 E2
 
although  structures  can  oVen  be  determined,  soluEon  exchange  is  oVen  too  fast  for  the  
NMR  Eme  scale  (≤  ms)  except  at  low  temperatures  
 
Examples  of  fluxional  molecules:  
Fe(CO)5    only  one  13C  resonance  
 PF5    only  one  19F  resonance  
CN 5 TBP vs SP
 
only  a  small  energy  difference  exists  between  the  structural  extremes  
 
 
CN  6    octahedral    90,  180°    
 
the  most  common  and  thus  most  important  CN    
 
 
                          L        TiCl64-­‐    
      L       L      W(CH3)6  
  M
  L L
  L
 
 
               
               
          L      
 
L
            L      Co(en)33+  
  M
      L       L      chiral  
  L
   
 
CN 6 Oh D3

L L
L L L L
M M
L L L L
L L

nearly all six coordinate complexes approach or possess octahedral

structures rather than the alternative trigonal prismatic (D3h) structure

D3h  
COMMON COORDINATION NUMBERS AND GEOMETRIES

CN  2   linear  

L
CN  3   L M trigonal   T-­‐shaped  
L

CN  4   square  
tetrahedral  
planar  

CN  5   trigonal   square  
equatorial
bipyramidal   pyramidal  

CN  6   octahedral  
Structural distorsions

structures rigorously adhering to the highest possible symmetry

for a given MLn complex are rare, even with identical ligands

distortions to lower symmetries are common

ML5 equilibrium between TBP and SP – nonstatic

ML6 Oh to D4h by elongation or compression of trans ligands

L
L
M
L common distortion sources
L L
L L ligand stereochemistry
L
M
L
crystal packing
L
L L Jahn-Teller effect
L
L L
M
fluxional or nonrigid structures
L L

L
Higher coordination numbers: 7 – 12
complexes with CNs exceeding six often contain third series or inner transition metals
Higher coordination numbers: 7 – 12
complexes with CNs exceeding six often contain third series or inner transition metals
CN  7    pentagonal  bipyramidal    
 
     L          
  L
  L
L M VF73-­‐  
 
L
  L
  L
     
     
   monocapped  octahedral                
  TaF72-­‐  
               
 
 
 
     
   monocapped  trigonal  prism  

NbF72-­‐  
CN  8    cubic            
 
L L
 
L   each  ligand  is  projected  to  the    
    M   L    
corners  of  a  cube  –  rare  in  
  L L
coordina9on  compounds,  
     L L
common  in  laQces  
 
 
 
   square  an9prisma9c      
     
L
    L     L     one  half  of  cube  twisted  45°  
 
  L M L
      TaF83-­‐  
    L L
    L
 
   trigonal  dodecahedral    
      Mo(CN)83-­‐  
L L
 
square  an9prisma9c  and  
    L   M      L
dodecahedral  structures  oRen  
L L are  of  similar  energy  
L L  
CN  9-­‐12  common  only  for  the  lanthanides  and  ac9nides  
 
 
 
 
 
   
   
 
   
CN in close-packed lattices
metals in close-packed lattices can have CN of 12

close-­‐packed  labces  result  in  formaEon  of  both  octahedral  (CN  6)  and  tetrahedral  (CN  4)  
holes
CN in close-packed lattices
Binary solids  

ions  in  close-­‐packed  labces  oVen  have  a  CN  of  6  (e.g.,  NaCl)  or  8  (e.g.,  CsCl),  depending  on  
the  relaEve  size  of  the  ions
CN in close-packed lattices    
 
 
In  solids  of  the  general  formula  ABO3,  CN  of  12  for  A  and  CN  of  6  for  B  
   
 
 
Common vs uncommon coordination numbers

CN range from 1 to 12, but the most common ones are 4, 6, 8 and 12, with 6 being most
prevalent

Why are certain CN more common?

They represent a balance between stabilization due to bond formation and destabilization due to
ligand-ligand repulsion

if a TM complex of CN 3, 5 or 7 increases its CN by 1, or if a CN 10 complex

increases its CN by 2, the increase in the total bond energy of the complex is
not generally accompanied by a large change in the M – L bond distances

the large gain in total bond energy compensates for the

increase in interligand repulsion
 
Common vs uncommon coordination numbers

CN range from 1 to 12, but the most common ones are 4, 6, 8 and 12, with 6 being most
prevalent

Why are certain CN more common?

They represent a balance between stabilization due to bond formation and destabilization due to
ligand-ligand repulsion

if a complex of CN 5, 7 or 9 decreases its CN by 1, the loss in total bond energy

is often accompanied by a relatively large change in M – L bond distances, with
ligands approaching the metal center more closely

the decrease in interligand repulsion compensates for the

decrease in total bond energy and ligands come closer to the metal center
Common vs uncommon coordination numbers

CN range from 1 to 12, but the most common ones are 4, 6, 8, and 12 with 6 being most
prevalent

Why are certain CN more common?

They represent a balance between stabilization due to bond formation and destabilization due to
ligand-ligand repulsion

Complexes of CN other than 4, 6, 8 or 12 tend to lose or gain ligands

relatively easily and thus are relatively rare

Uncommon CN tend to be unstable to bond formation (low ligand repulsion)

or bond cleavage (high ligand repulsion)
Generalizations on coordination numbers
high coordination numbers

large metal size and/or high oxidation states; small, hard ligands

low coordination numbers

small metal size and/or low oxidation states; large, soft ligands

metal-metal bonding
multiple ligand-metal bonding
NUCLEARITY and METAL CLUSTERS

[MxLn]z z = complex charge x = nuclearity

mononuclear [MLn]z

binuclear [M2Ln]z

trinuclear [M3Ln]z

etc.
BINUCLEAR SPECIES
 
   
 
BRIDGING LIGANDS

µ-Cl

terminal  

µ3-Cl

TRINUCLEAR SPECIES
 
   
 
TETRANUCLEAR SPECIES
 
   
 
HEXANUCLEAR SPECIES
 
   
 
 High nuclearity

[Mn84O72(O2CMe)78(OMe)24(MeOH)12(H2O)42(OH)6]·xH2O·yCHCl3

A. J. Tasiopoulos, A.Vinslava, W. Wernsdorfer, K. A. Abboud, G. Christou Angew. Chem. Int. Ed. 2004, 43, 2117

Isomerism
Isomers (from Greek, ‘sharing equally’) are compounds  with  the  same  formula  but  a  
different  arrangement  of  atoms  in  the  molecule  (and  different  properEes)  

Stereoisomers are molecules with the same empirical formula and atom-to-atom bonding
sequence but differing in atomic spatial arrangements.
Isomers of this type can be
geometric isomers (diastereoisomers)
or
optical isomers (enantiomers)

Structural isomers are molecules with the same empirical formula but different atom-to-
atom bonding sequences (connectivity)

What  type  of  isomers  are  related  tetrahedral  and  square  planar  complexes?  
cis/trans isomerism in square planar complexes
DIASTEREOMERS  
  -­‐  CN  4  

Pt(n-­‐Pr3P)2Cl2    

Cl P(n-Pr)3 Cl P(n-Pr)3
Pt Pt
Cl P(n-Pr)3 (n-Pr) 3P Cl
cis trans

NiCl42-­‐  

Cl
Cl Cl
Ni Ni
Cl Cl
Cl Cl Cl
K+  salt   Ph4As+  salt  

Note:  In  soluEon  NiCl42-­‐  is  tetrahedral  

DIASTEREOMERS  
  -­‐  CN  4  

No  isomers  for  MA4  and  MA3B  

DIASTEREOMERS  
  -­‐  CN  4  
ENANTIOMERS  
  -­‐  CN  4  
DIASTEREOMERS  
  –  CN  6  octahedral  
DIASTEREOMERS  
  –  CN  6  octahedral  
CN 6 Geometric isomers  

cis/trans  isomerism  in  [CoCl2(NH3)4]+  

facial/meridional  isomerism  in  CoCl3(NH3)3  

ENANTIOMERS  
  –  CN  6  octahedral  
ENANTIOMERS  –  CN  6  octahedral  
 
nonsuperimosable  mirror  images  
 
 
Structural  labels:  
clockwise  rotaEon  (Δ, delta)    
counterclockwise  rotaEon  (Λ, lambda)    
 
 
Experimental  labels  for  polarized  light  
rotaJon:  
clockwise  rotaEon  –  d-­‐isomer  or  (+)-­‐
isomer  
 
counterclockwise  rotaEon  –    l-­‐isomer  or  
(–)-­‐isomer  
ENANTIOMERS  –  CN  6  octahedral  
       

[Mn(acac)3]  enanFomers  
STEREOISOMERS  
  –  CN  6  octahedral