CHM 122 Wk 12, II Isomers It is possible (actually fairly common, especially in organic chemistry) for two compounds (or complexes) to have the same formula, yet NOT be the same chemical substance (or species). How can you tell? At least one property is different! (You can tell operationally) How can this be? ANS: Something is different about the way the atoms in the species are “arranged”. There can be MANY ways for this to happen! Different Connections between atoms (different bonds) Same connections, but different arrangement in space Two compounds (species) are called isomers if they have the same formula but are not the “same”

Different “ways” to be isomers (very comparable to Tro, Fig. 24.6) CHM 122 Wk 12, II Different “ways” to be isomers (very comparable to Tro, Fig. 24.6) Structural Optical Isomers or Coordination Isomers Geometric Isomers  cis-trans  same ligand, but connected via a different atom  anionic ligand swaps with counter(an)ion  will occur if species is “chiral” (no plane of symmetry)  other “geometrical”  for salts only Omit in S’13

CHM 122 Wk 12, II Example of Linkage Isomers (a type of Structural Isomerization) *The same ligand is attached, but via a different atom Co(NH3)5(NO2)2+ Co(NH3)5(ONO)2+ donor atom

Coordination Isomers (the other kind of Structural type of isomer(s)) CHM 122 Wk 12, II Coordination Isomers (the other kind of Structural type of isomer(s)) The word “coordination” implies that “somebody different is coordinating” (not just a different atom, but a different ligand). [still a different “connection” or bond] How can there be a different ligand if the formula must be the same? ANS: You move a ligand “out” and put a counterion* “in”. I called this “swapping” Unlike linkage isomers (in which no counterions need be shown), one can only have coordination isomers with coordination compounds that are salts (i.e., counterions must be present/shown) *You can also swap ligands in the special case in which both the cation and anion are metal complex ions. See later 

Coordination Isomers (continued) CHM 122 Wk 12, II Coordination Isomers (continued) You can check to see if you have coordination isomers by considering the dissociation in water. When complex is dissolved in water, the complexes will have a different formula (only the “compounds” are isomers here) Remember, you cannot swap a neutral ligand with a counter anion!!!!

Coordination Isomers (examples) CHM 122 Wk 12, II Coordination Isomers (examples) [Co(NH3)4Cl2]Br and [Co(NH3)4ClBr]Cl [Co(NH3)4Cl2]Br  Co(NH3)4Cl2+ + Br - [Co(NH3)4ClBr]Cl  Co(NH3)4ClBr+ + Cl- [Co(en)2Cl2]ox and [Co(en)2(ox)]Cl2

Coordination Isomers (different kind of example) CHM 122 Wk 12, II Coordination Isomers (different kind of example) *As noted earlier, in the special case in which both the cation and anion are metal complexes, one can get coordination isomers by simply swapping ligands. The key is that the ligands coordinating to each metal are now different. Different “connection” [Ru(en)3][Fe(CN)6] & [Ru(en)2(CN)2][Fe(en)(CN)4] 1st dissociates, get: Ru(en)33+ and Fe(CN)63- 2nd dissociates, get: Ru(en)2(CN)2+ and Fe(en)(CN)4-

Two Families of Stereoisomer CHM 122 Wk 12, II Two Families of Stereoisomer In both, all bonds are the same, but something is different about the relative positions of the atoms in space Geometric: not mirror images Relative spatial position of atoms is different Cis-trans, or other “geometric” isomer Optical (Enantiomers) : ARE mirror images Relative spatial position of atoms is same, except “inverted” (mirror image)

Example of (one kind of) Geometric Isomerism (cis-trans type) CHM 122 Wk 12, II Example of (one kind of) Geometric Isomerism (cis-trans type) All bonds same, but relative spatial arrangement differs (Cl’s 90° vs 180° degrees “apart“)

Cis-trans isomerization can occur in octahedral geometry also CHM 122 Wk 12, II Cis-trans isomerization can occur in octahedral geometry also cis trans

CHM 122 Wk 12, II Orientation Needs to Be Considered! If structures are superimposable (i.e., identical), then not isomers Both are cis (identical) Both are trans (identical)

Not all complexes have a geometrical isomer! CHM 122 Wk 12, II Not all complexes have a geometrical isomer!

Yet another kind of Geometric Isomer Pair (not cis-trans)* CHM 122 Wk 12, II Yet another kind of Geometric Isomer Pair (not cis-trans)* Same # and type of each bond, but different relative spatial arrangement of atoms *Tro (correctly) calls these “fac” and “mer”. You do not need to know these names, but just be able to recognize that these are geometric isomers

CHM 122 Wk 12, II The following three slides are not needed for S’13, but I am including them for completeness

Enantiomers and “Chirality” CHM 122 Wk 12, II Enantiomers and “Chirality” A molecule or complex is chiral if There is NO plane of symmetry Its mirror image is NOT the same structure (i.e., NOT superimposable A molecule or complex is achiral if There IS one (or more) plane of symmetry Its mirror image IS the same exact structure (i.e., superimposable) Enantiomers are isomers that are mirror images, THUS: If a structure IS chiral, it WILL have an enantiomer If a structure is achiral, it will NOT have an enantiomer

Enantiomers and Chirality--Examples CHM 122 Wk 12, II Enantiomers and Chirality--Examples achiral => mirror image is identical, so no enantomer chiral => has a mirror image that is not identical

CHM 122 Wk 12, II