Chapter 19: Phenomena
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1 Chapter 19: Phenomena Phenomena: Transition metal complexes are often used in paints for coloration due to their wide range of colors. Using the data below identify any patterns in the colors of compounds. Compound Compound Color of Compound Color Absorbed by Compound Energy Splitting 1 [Co(H 2 O) 6 ]Cl 3 Blue Orange 184 kj mol 2 [Co(NH 3 ) 6 ]Cl 3 Yellow Violet 266 kj mol 3 [Co(NH 3 ) 5 (H 2 O)]Cl 3 Red Green 228 kj mol 4 [Co(H 2 O) 6 ]Br 3 Blue Orange 184 kj mol 5 [Ni(NH 3 ) 6 ]Cl 2 Blue Orange 200 kj mol 6 [Ni(H 2 O) 6 ]Cl 2 Green Red 177 kj mol 7 [CoCl(NH 3 ) 5 ]Cl 2 Violet Yellow 214 kj mol 8 [CoCl 2 (NH 3 ) 4 ]Cl Green Red 172 kj mol 9 [Fe(H 2 O) 6 ]Cl 2 Green Red 173 kj mol 10 [Fe(H 2 O) 6 ]Cl 3 Yellow Violet 300 kj mol
2 Big Idea: The properties of d- block metals are governed by the availability of d-orbitals and their variable valence electrons. The physical properties of d-block complexes depends on the properties of the ligands bound to the metal. Chapter 19 Transition Metals & Coordination Chemistry o The d-block Elements and Their Compounds o Coordination Compounds o Crystal Field Theory o Ligand Field Theory 2
3 d-block Elements and Their Compounds 3 Transition metals, are located in groups 3 through 11. They are called transition metals because they transition between the highly reactive s block metals and the much less reactive metals of group 12 and the p block.
4 d-block Elements and Their Compounds Scandium (Sc) Titanium (Ti) Vanadium (V) Chromium (Cr) Facts Reacts vigorously with water Resistant to corrosion (protective oxide skin) Requires strong reducing agent for extraction from, its ores Vanadium compounds come in a wide range of color due to its many oxidation states Corrosion resistant Uses Few uses Not essential to life Jet engines Dental applications Makes tough steel for automobile and truck springs Stainless steel Chrome plating Glazes for ceramics 4
5 d-block Elements and Their Compounds Facts Manganese (Mn) Not as corrosion resistant as chromium but more corrosion resistant than iron Iron (Fe) Cobalt (Co) Nickel (Ni) Most widely used d metal Most abundant element on earth Uses Alloying with steel Main component in steel (next biggest component C up to 2.1%) Essential to life Alloying with steal Used to make permanent magnets found in speakers Essential to life 70% of the western world s nickel comes from ore that was brought close to the earth surface nearly 2 billion year ago by the violent impact of a huge meteor Used to make stainless steal Nickel is alloyed with copper to make nickel coins 5
6 d-block Elements and Their Compounds Facts Copper (Cu) One of the coinage metals High conductivity Corrosion resistant Zinc (Zn) Corrosion resistant Uses Alloying: Brass (Cu + Zn) and Bronze (Cu and Sn) Used for electrical wires Used for water pipes Used for galvanizing 6
7 d-block Elements and Their Compounds 7 The shape of the d-orbitals affect the properties of transition metals. The d-orbital lobes are far apart and so only weakly repel each other. The d-orbitals have low electron density near the nucleus therefore are not very effective at shielding.
8 d-block Elements and Their Compounds Orange boxes are common oxidation numbers. Green boxes are other know states. 8 Most d-block metals have more that one oxidation state other than 0. Elements close to the center of the row have the widest range of oxidation numbers.
9 d-block Elements and Their Compounds Note: The ordering of the ns and (n-1)d energy level shifts once the (n-1)d orbitals contain e - causing the (n-1)d e - to be lower in energy than the ns electrons. Therefore, ns electrons are lost before (n-1)d electrons when forming transition metal ions. ns electrons are also lost before (n-2)f electrons. 9
10 d-block Elements and Their Compounds Student Question What is the correct electron configuration for Ir 3+? a) [Xe]4f 13 5d 7 b) [Xe]6s 2 4f 14 5d 7 c) [Xe]4f 14 5d 6 d) [Xe]6s 2 4f 14 5d 4 e) None of the Above 10
11 Coordination Compounds Complex Ion: A charged species consisting of a metal ion surrounded by ligands. Ligand: A group attached to a central metal ion in a complex. Central grey atom is transition metal. Colored atoms ligands. # # # # Examples: [Fe(H 2 O) 6 ] 3+ [CoCl 4 ] 2- [NiBr 4 ] 2- [Ag(NH 3 ) 2 ] + Note: Complex ions are written inside brackets. If ligands are bound to a metal but the species formed is not an ion the system is still written in brackets ex: [Hg(CH 3 ) 2 ]. Note: Complex ions do not dissociate in solution. 11
12 Coordination Compounds Formula H 2 O NH 3 Br - Cl - CN - CO NH 2 CH 2 CH 2 NH 2 OH - I - CH 3 NH 2 NO 2- (N bonded to metal) ONO - (O bonded to metal) NO C 2 O 4 2- SO 4 2- SCN - Name Aqua Ammine Bromo Chloro Cyano Carbonyl Ethylenediamine (en) Hydroxo Iodo Methylamine Nitro Nitrito Nitrosyl Oxalato (ox) Sulfato Thiocyanto Chelate: A complex containing at least one polydentate ligand that forms a ring of atoms. Note: Bidentate ligands form 2 bonds to the metal ion. 12
13 Coordination Compounds Coordination Number: The number of bonds formed between the metal ion and the ligands in a complex ion. # # # # What is the coordination number for: Shape Octahedral Tetrahedral Square Planar Linear Coordination Number 13
14 Coordination Compounds Student Question Determine the coordination number and oxidation number, respectively, of the transition metal ion[crbr 2 (en) 2 ] +? a) 4, 3 b) 4, 2 c) 6, 3 d) 6, 2 e) None of the Above 14
15 Coordination Compounds Coordination Compound: A compound composed of a complex ion and counter ion sufficient to give no net charge. Counter Ion: Anions or cations that balance the charge on the complex ion in a coordination complex. Example: K 3 [Fe(CN) 6 ] K + counter ion [Fe(CN) 6 ] 3- complex ion Note: Counter ions can dissociate in water (ionically bonded) while complex ions can not dissociate in water (covalently bonded). 15
16 Coordination Compounds Student Question How many of the following coordination compounds will form a precipitate when treated with an aqueous solution of AgNO 3? [CrCl 3 (NH 3 ) 3 ] [Cr(NH 3 ) 6 ]Cl 3 [CrCl(NH 3 ) 5 ](OH) 2 Na 3 [Cr(CN) 6 ] a) 0 b) 1 c) 2 d) 3 e) 4 16
17 Coordination Compounds Naming Coordination Complexes 1. Cations (positively charged) are named before the anions (negatively charged). 2. Name the ligands first and then the metal atom or ion. When writing the chemical formula of complex ions the metal comes first. 3. Most neutral ligands have the same name as the molecule. Example: NH 2 CH 2 CH 2 NH 2 (ethylenediamine) Exceptions: H 2 O aqua CO carbonyl NH 3 ammine NO nitrosyl Anionic ligand (- charged) end in o; -ide (such as chloride) change to o (chloro) -ate (such as sulfate) change to ato (sulfato) -ite (such as nitrite) change to ito (nitrito)
18 Coordination Compounds Naming Coordination Complexes (Continued) 5. Greek prefixes indicates the number of each type of ligands in the complex di- tri- tetra- penta- hexa- Note: If the ligand already contains a Greek prefix (ethylenediamine) or if it is polydentate (able to attach at more than one binding site) then use the following prefixes instead. In addition, the name of the ligand is put in parenthesis bis- tris- tetrakis- 6. The oxidation state of the central metal ion is designated by a Roman numeral in parentheses. 18
19 Coordination Compounds Naming Coordination Complexes (Continued) 7. When more than one ligand is present, the ligands are named in alphabetical order (not including Greek prefixes). 8. If the complex has an overall negative charge (the suffix ate is added to the stem of the metal s name). a. If the symbol of the metal originates from Latin and it has an overall negative charge the Latin name is used for the metal. Examples: Metal Anionic Complex Base Name Metal Anionic Complex Base Name Iron Ferrate Silver Argentate Copper Cuprate Gold Aurate Lead Plumbate Tin Stannate 19
![Coordination Compounds Name The Compound: [Ag(NH 3 ) 2 ][Ag(CN) 2 ] Cation: [Ag(NH 3 ) 2 ]? Anion: [Ag(CN) 2 ]?](/docs-images/74/70681938/images/20-0.jpg "Determine Possible Ions Possible Ag ions: Ag +, Ag 2+, and Ag 3+ x(charge on Ag cat ) = -(-2(from CN - )+ y(charge on Ag an ) x y 1")
20 Coordination Compounds Name The Compound: [Ag(NH 3 ) 2 ][Ag(CN) 2 ] Cation: [Ag(NH 3 ) 2 ]? Anion: [Ag(CN) 2 ]? Determine Possible Ions Possible Ag ions: Ag +, Ag 2+, and Ag 3+ x(charge on Ag cat ) = -(-2(from CN - )+ y(charge on Ag an ) x y 1 x=-(-2+1) 2 x=-(-2+2) 3 x=-(-2+3) 20
21 Coordination Compounds Isomers Same Number and Type of Atoms Structural Isomers o Different Bonds o Different Chemical Formulas o Different Name Linkage Isomers Coordination Isomers Stereoisomers o Same Bonds o Different Orientations o Same Chemical Formulas o Different Name Geometric Isomers Optical Isomers 21
22 Coordination Compounds Types of Structural Isomers: Linkage Isomers: Isomers in which atoms or groups of atoms can assume different position around a rigid bond. Example: [CoCl(NO 2 )(NH 3 ) 4 ] + and [CoCl(ONO)(NH 3 ) 4 ] + (bonding atom written first) Coordination Isomers: Isomers that differ by the exchange of one or more ligands between cationic complex and an anionic complex. Example: [Cr(NH 3 ) 6 ][Fe(CN) 6 ] and [Fe(NH 3 ) 6 ][Cr(CN) 6 ] 22
23 Coordination Compounds Types of Sterioisomers: Geometric Isomers: Isomers in which atoms or groups of atoms can assume different positions around a rigid bond. Note: Geometric Isomers are also sometimes referred to as cis trans isomers. Cis: Ligands are on the same side. Trans: Ligands are on the opposite side. Trans Cis 23
24 Coordination Compounds Student Question How many geometric isomers of the square planar complex [PtBrCl(NH 3 )(H 2 O)] are possible? a) 1 b) 2 c) 3 d) 4 e) None of the Above 24
25 Coordination Compounds Types of Stereoisomers: (Continued) Optical Isomers: Isomers in which one molecule is the mirror image of the other molecule. Chiral Complex: A complex that is not identical with its mirror image. Note: If something is chiral it will have an optical isomer. Note: If the mirror image is identical to the starting configuration, they are not considered optical isomers. Achiral Complex: A complex that is identical to its mirror image. Note: If something is achiral it will not have an optical isomer. Enantiomers: A chiral complex and its mirror image. 25
26 Coordination Compounds Student Question How many complex species will exhibit optical isomerism? [CoCl 4 (en)] - trans-[crbrcl(en) 2 ] + cis-[cocl 2 (NH 3 ) 4 ] + cis-[crbr 2 (ox) 2 ] - cis-[cocl 3 (NH 3 ) 3 ] a) 0 b) 1 c) 2 d) 3 e) 4 26
27 Crystal Field Theory Octahedral Complexes: e g -orbitals Which orbitals are lower in energy? 27 t 2g -orbitals Energy In crystal field theory one assumes that the ligands can be represented by negative point charges and that the metal is a positive point charge located at the center of the system. One then examines how these negative point charges interact with the d orbitals.
28 Crystal Field Theory Tetrahedral Complexes: e g -orbitals Which orbitals are lower in energy? Energy t 2g -orbitals 28
29 Crystal Field Theory Electromagnetic Spectrum Determining Color Absorbed ~ Wavelength Color nm Red nm Orange nm Yellow nm Green nm Blue nm Violet Observed Red Orange Yellow Green Blue Violet Adsorbed Green Blue Violet Red Orange Yellow 29
30 Crystal Field Theory Student Question Reaction 6H 2 O + NiSO 4 [Ni(H 2 O) 6 ] 2+ + SO 2-4 [Ni(H 2 O) 6 ] NH 3 [Ni(NH 3 ) 6 ] H 2 O [Ni(NH 3 ) 6 ] en [Ni(en) 3 ] 2+ +6NH 3 Observed Color Absorbed Color Put the ligand in order from smallest crystal field splitting to largest: a) en < NH 3 < H 2 O b) NH 3 < en < H 2 O c) en < H 2 O < NH 3 d) H 2 O < NH 3 < en e) None of the above 30
31 Crystal Field Theory Large Splitting Small Splitting Different ligands affect the d orbitals of a given metal ion to different degrees and thus produce different values of the ligand field splitting. The spectrochemical series arranges ligands according to the relative magnitudes of the ligand field splitting that they produce. 31
32 Crystal Field Theory Student Question Predict the number of unpaired electrons of an octahedral d 7 complex with a strong field ligands and weak field ligands respectively. a) 1, 3 b) 3, 1 c) None of the above 32
33 Crystal Field Theory Octahedral Complexes: e g -orbitals Which orbitals are lower in energy? 33 t 2g -orbitals Energy In crystal field theory one assumes that the ligands can be represented by negative point charges and that the metal is a positive point charge located at the center of the system. One then examines how these negative point charges interact with the d orbitals.
34 Ligand Field Theory Which orbitals are considered? 6 orbitals (1 orbital from each of the 6 ligands) come from the ligands. 9 orbitals (1 s orbital, 3 p orbitals, and 5 d orbital) come from the d-metal. Giving a total of 15 molecular orbitals. Where do the electrons come that fill the molecular orbitals? The electrons from the ligands (12 e - ) fill up all of the bonding ` orbitals, leaving the electrons from the metal to fill the nonbonding and antibonding orbitals. 34
35 Ligand Field Theory Weak Field Ligand If the t 2g orbital is closer in energy to the π bonding orbital, the two orbitals will interact and the electron in the filled π orbitals will enter the lower energy molecular orbital therefore the electrons in the d-metal will have to occupy the higher energy molecular orbital which will decrease the octahedral field splitting. This is what happens for weak field ligands. 35
36 Ligand Field Theory Strong Field Ligand If however the t 2g orbitals are closer in energy to the π antibonding orbital when the two orbitals interact, there are no electrons from the ligand to go into the lower energy molecular orbital. Therefore the electrons in the metal can enter the lower energy orbital and the octahedral field splitting will increase. This is what happens for strong field ligands. 36
37 Take Away From Chapter 19 Big Idea: The properties of d-block metals are governed by the availability of d-orbitals and their variable valence. The physical properties of d-block complexes depends on the properties of the ligands bound to the metal. The d-block Elements and Their Compounds Know that the shape of the d-orbital and the number of d electrons affects the physical properties of transition metals Know the shape of d-orbitals Be able to write out the electron configuration for transition metals and their ions (6,7) 37 Numbers correspond to end of chapter questions.
38 38 Take Away From Chapter 19 Coordination Compounds (16) Be able to determine the coordination number of coordination compounds Be able to determine the number of bonding sites on a ligand (32) Be able to name coordination compounds (22,23,24,25,26) Know that only counter ions dissociate not ligands when put into solution Be able to determine the coordination compound from experimental data (27,71) Be able to recognize different types of isomers (31,40) Structural (37) Linkage (39) Coordination Stereoisomers (42) Geometric (33,34) Optical Numbers correspond to end of chapter questions.
39 Take Away From Chapter 19 Crystal Field Theory Know octahedral and tetrahedral d-orbital spitting (46) Know the effects of strong and weak field ligands (45,51,53) High Spin (weak field) Low Spin (strong field) Be able to predict magnetic properties (52,56) Diamagnetic (pair e - ) Paramagnetic (unpaired e - ) Be able to determine d-orbital splitting (50,57) = hc λ Ligand Field Theory 39 Numbers correspond to end of chapter questions.
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