p.1
Ligands and Their Types
What is a ligand?
A molecule or ion having a lone electron pair that can be used to form a bond to a metal ion (Lewis base).
p.1
Ligands and Their Types
What is a coordinate covalent bond?
A bond formed between a metal and a ligand.
p.3
Coordination Numbers and Geometries
Which geometries are commonly associated with coordination number 8?
The geometries commonly associated with coordination number 8 are square antiprismatic and dodecahedral.
p.2
Chelating Agents and Their Applications
What do chelating agents do?
Bind to metal ions removing them from solution.
p.3
Coordination Numbers and Geometries
What is the coordination number of a complex ion that can accommodate 8 ligands?
The coordination number that can accommodate 8 ligands is 8.
p.11
Crystal Field Theory and Ligand Field Theory
Who proposed the Crystal Field Theory and in what year?
Hans Bethe proposed the Crystal Field Theory in 1929.
p.7
Magnetic Properties of Complexes
How many unpaired electrons does the complex [CoF6]3- have?
It has four unpaired electrons, making it paramagnetic and categorized as a high-spin complex.
p.7
Valence Bond Theory and Hybridization
How is the number of d electrons for cobalt calculated?
The number of d electrons is calculated as AN of central metal - number of electrons lost - AN of previous inert gas. For Co: 27 - 3 - 18 = d6.
p.47
Chelating Agents and Their Applications
What happens to Ni 2+ and Pd 2+ in the presence of dimethyglyoxime?
They form insoluble colored precipitates.
p.9
Coordination Numbers and Geometries
What are the limitations of hybridization in explaining certain properties of complexes?
Hybridization does not account for the splitting of d-orbitals, the spectra of complexes, reaction rates, mechanisms, or the distinction between outer and inner fields.
p.33
Crystal Field Theory and Ligand Field Theory
What are the consequences of crystal field splitting in transition metal complexes?
The consequences include changes in electronic configuration, variations in magnetic properties, and differences in color of complexes due to the energy differences between split d-orbitals.
p.14
Crystal Field Theory and Ligand Field Theory
What effect do discrete point charges (ligands) have on the d-orbitals in an octahedral field?
The degeneracy of the d-orbitals is removed, and different orbitals interact with the charges to varying extents.
p.32
Crystal Field Theory and Ligand Field Theory
What is the energy relationship between orbitals that come in direct contact with ligand fields and those that slide past it in square planar coordination?
Orbitals that come in direct contact with the ligand fields will have higher energies than orbitals that slide past the ligand field and have more of indirect contact.
p.54
Coordination Numbers and Geometries
What is the coordination complex represented by [Ni(CN)4]2-?
It is a nickel complex with four cyanide ligands.
p.43
Stability of Complex Compounds
What does the formation constant (Kf) describe in complex compounds?
The formation constant (Kf) describes the formation of a complex ion from a central metal and the ligands attached to it.
p.63
Valence Bond Theory and Hybridization
What contributes to the stability of cyclic carbon fragments?
Cyclic carbon fragments with double bonds (C=C - C) are extra stable due to aromaticity.
p.14
Crystal Field Theory and Ligand Field Theory
Which d-orbitals are destabilized more in an octahedral field?
The d-orbitals along the axes are destabilized more than those that lie between the axes.
p.57
Organometallic Compounds and Their Importance
What is the role of Grignard reagents in organic synthesis?
Grignard reagents are used to form new carbon-carbon bonds by reacting with carbonyl compounds, enabling the synthesis of alcohols and other organic molecules.
p.4
Coordination Numbers and Geometries
What is the coordination number and geometry of the complex [Ag(NH3)2]+?
The coordination number is 2 and the geometry is linear (sp hybridization).
p.17
Crystal Field Theory and Ligand Field Theory
What is the orbital occupancy for low-spin complexes of d4 through d7 metal ions?
Low-spin complexes occur with strong-field ligands.
p.16
Magnetic Properties of Complexes
What does Hund's rule predict for d1-d3 systems regarding electron pairing?
Hund's rule predicts that the electrons will not pair and occupy the t2g set.
p.30
Crystal Field Theory and Ligand Field Theory
What is the equation representing the relationship between the electron populations in eg and t2g orbitals?
-0.6 x n(e g ) + 0.4 x n(t2g) = 39
p.11
Crystal Field Theory and Ligand Field Theory
How does Crystal Field Theory describe bonding in coordination compounds?
It considers bonding as an electrostatic attraction between a positively charged nucleus and the electrons of the ligands, with a focus on the d-electrons of the metal ion.
p.34
Ligands and Their Types
What is the impact of ligand type on the ionic radii of transition metal complexes?
Different ligands can cause varying degrees of steric and electronic effects, which can either increase or decrease the ionic radii of the transition metals in the complexes.
p.14
Crystal Field Theory and Ligand Field Theory
What happens to the d-orbitals in the presence of a spherically symmetric field of negative charges?
The d-orbitals remain degenerate but are raised in energy due to repulsion with negative charges.
p.20
Crystal Field Theory and Ligand Field Theory
How does the ligand affect splitting energy?
The effect of the ligand on splitting energy increases with stronger ligands leading to higher Δ.
p.49
Chelating Agents and Their Applications
What is chelate therapy used for?
To treat problems caused by the presence of metals in toxic proportions in plant/animal systems.
p.53
Coordination Numbers and Geometries
What is another name for Werner's Theory?
Werner's Theory is also known as the coordination theory of complex compounds.
p.49
Chelating Agents and Their Applications
Which ligands are used to remove excess copper and iron?
D-penicillamine and desferrioxime B via the formation of coordination compounds.
p.29
Crystal Field Theory and Ligand Field Theory
What is the Crystal Field Stabilization Energy (CFSE) for tetrahedral complexes?
CFSE = -0.4 x n(t2) + 0.6 x n(e)
p.17
Crystal Field Theory and Ligand Field Theory
What is the orbital occupancy for high-spin complexes of d4 through d7 metal ions?
High-spin complexes occur with weak-field ligands.
p.55
Ligands and Their Types
What defines a Lewis acid and a Lewis base?
A Lewis acid is an electron pair acceptor, while a Lewis base is an electron pair donor.
p.10
Crystal Field Theory and Ligand Field Theory
What concept serves as the core explanation for the electronic structure of metal complexes in inorganic chemistry?
Crystal Field Theory (CFT)
p.4
Valence Bond Theory and Hybridization
What does Valence Bond Theory predict about metal complex bonding?
It predicts that metal complex bonding arises from the overlap of filled ligand orbitals and vacant metal orbitals, resulting in a coordinate covalent bond.
p.5
Magnetic Properties of Complexes
How many unpaired electrons are present in the tetrahedral copper complex CuCl4^2-?
One unpaired electron, making it paramagnetic and attracted by magnets.
p.44
Applications of Coordination Compounds
What are the main areas where coordination compounds play an important role?
Coordination compounds are important in analytical chemistry, metallurgy, biological systems, industry, and medicine.
p.28
Crystal Field Theory and Ligand Field Theory
How does the splitting of d orbitals in tetrahedral complexes compare to that in octahedral complexes?
The splitting of d orbitals in tetrahedral complexes is the reverse of that observed in octahedral complexes.
p.46
Applications of Coordination Compounds
What color complex is formed when Co is present?
The presence of Co can be detected by the formation of a blue color thiocyanate complex.
p.46
Applications of Coordination Compounds
What color complex is formed with Fe?
The presence of Fe can be detected by the formation of a blood red color thiocyanate complex.
p.2
Chelating Agents and Their Applications
How do phosphates function in water treatment?
They tie up Ca 2+ and Mg 2+ in hard water to prevent them from interfering with detergents.
p.11
Crystal Field Theory and Ligand Field Theory
What modifications did J.H. Van Vleck propose in 1935 regarding Crystal Field Theory?
J.H. Van Vleck proposed modifications to allow for some covalency in the interactions, referred to as Ligand Field Theory.
p.9
Valence Bond Theory and Hybridization
What is the main difference between sp3d2 and d2sp3 hybrids?
The difference lies in the principal quantum number of the d orbital; sp3d2 hybrids have the same principal quantum number for s, p, and d orbitals, indicating High Spin, while d2sp3 hybrids have a principal quantum number of the d orbitals that is one less than that of s and p orbitals, indicating Low Spin.
p.13
Crystal Field Theory and Ligand Field Theory
What determines how ligands interact with d orbitals in octahedral complexes?
The relative orientation of the orbital and the ligand determines the interaction strength.
p.63
Valence Bond Theory and Hybridization
What is special about carbon in terms of bonding?
Carbon readily forms strong bonds with other carbon atoms (C-C) and strong multiple bonds (C=C), as well as very strong bonds with hydrogen (H).
p.55
Ligands and Their Types
How are ligands and metals classified in terms of Lewis acid/base theory?
Ligands are considered Lewis bases, and metals are classified as Lewis acids.
p.64
Organometallic Compounds and Their Importance
What is the significance of the compound TiCl3 in Organometallic Chemistry?
It is used in Ziegler-Natta polymerization.
p.15
Crystal Field Theory and Ligand Field Theory
What is the relationship between the stabilization of the t2g set and the destabilization of the e g set in an octahedral field?
The t2g set must be stabilized as much as the e g set is destabilized to conserve the barycenter.
p.4
Coordination Numbers and Geometries
What is the coordination number and geometry of the complex [CoCl4]2-?
The coordination number is 4 and the geometry is tetrahedral (sp3 hybridization).
p.62
Organometallic Compounds and Their Importance
What type of bonds are observed in Group 2-11 organometallic compounds?
σ-bonds, π-bonds, δ-bonds, and η-bonds.
p.34
Coordination Numbers and Geometries
How does the oxidation state affect the ionic radii of transition metals?
Higher oxidation states generally lead to smaller ionic radii due to increased effective nuclear charge attracting the electrons more closely to the nucleus.
p.20
Spectrochemical Series and Color of Complexes
What is the order of strength of ligand interactions in the spectrochemical series?
Cl - < F - < H2O < NH3 < en < NO2 - < CN -
p.40
Crystal Field Theory and Ligand Field Theory
What does CFT neglect in its consideration of metal ion interactions?
CFT considers only the metal ion d-orbitals and ignores other metal orbitals such as s- and p-orbitals and ligand π-orbitals.
p.43
Stability of Complex Compounds
What are some experimental methods used to determine stability constants?
Methods include potentiometry, voltammetric methods (polarography and anodic stripping voltammetry), pH-metry, spectrophotometric methods, and nuclear magnetic resonance spectroscopy.
p.55
Ligands and Their Types
What is the significance of the coordination reaction between silver ions and ammonia?
It illustrates that the metal ion acts as a Lewis acid while the ligands function as Lewis bases.
p.39
Coordination Numbers and Geometries
What geometry is most favorable for four coordinated complexes?
Tetrahedral and square planar geometries are most favorable for four coordinated complexes.
p.52
Chelating Agents and Their Applications
Why can calcium and magnesium ions be selectively estimated during titration?
The selective estimation is possible due to the difference in the stability constants of calcium and magnesium complexes.
p.20
Coordination Numbers and Geometries
What is the d-electron configuration for Cr3+?
Cr3+ has a d3 electron configuration, calculated as 24-3-18.
p.48
Applications of Coordination Compounds
What coordination compound is responsible for photosynthesis?
Chlorophyll, which is a coordination compound of magnesium.
p.45
Chelating Agents and Their Applications
How can the purification of metals be achieved?
Purification of metals can be achieved through the formation and decomposition of their coordination compounds, such as converting impure nickel to [Ni(CO)4] and decomposing it to yield pure nickel.
p.47
Chelating Agents and Their Applications
What is the chemical reaction for the formation of the complex with Ni 2+ and HDMG?
Ni 2+ + 2 HDMG → [Ni(DMG) 2 ] + 2H +
p.43
Stability of Complex Compounds
What is indicated by a larger Kf value for a complex ion?
A larger Kf value indicates greater stability of the complex ion.
p.53
Coordination Numbers and Geometries
What does Werner's Theory explain?
Werner's Theory explains the formation of complex compounds.
p.52
Applications of Coordination Compounds
How is the hardness of water estimated?
The hardness of water is estimated by titration with the sodium salt of EDTA.
p.13
Crystal Field Theory and Ligand Field Theory
How do ligands interact with the lobes of d orbitals in octahedral complexes?
Ligands point directly at the lobes, leading to a stronger interaction.
p.46
Ligands and Their Types
What are some examples of reagents used for color reactions with metal ions?
Examples include EDTA, DMG (dimethylglyoxime), α–nitroso, β–naphthol, and cupron.
p.10
Crystal Field Theory and Ligand Field Theory
What are the more sophisticated models compared to Crystal Field Theory?
Ligand Field Theory (LFT) and Molecular Orbital Theory (MO)
p.33
Spectrochemical Series and Color of Complexes
What role does crystal field splitting play in determining the color of transition metal complexes?
Crystal field splitting determines the wavelengths of light absorbed, which influences the color observed by the observer; different ligands can cause different splits and thus different colors.
p.51
Applications of Coordination Compounds
What is an example of a coordination compound used as a catalyst for hydrogenation of alkenes?
Rhodium complex, [(Ph3P)3RhCl], known as the Wilkinson catalyst.
p.67
Ligands and Their Types
What does μx indicate in coordination chemistry?
μx indicates the presence of a bridging ligand between two or more metal centers, where x refers to the number of metal centers being bridged.
p.20
Magnetic Properties of Complexes
What type of spin state is associated with low spin complexes?
Low spin complexes are associated with stronger ligands that increase Δ.
p.39
Spectrochemical Series and Color of Complexes
What properties of transition metal complexes can Crystal Field Theory explain?
Crystal Field Theory can explain the color and spectral properties of many transition metal complexes.
p.69
Organometallic Compounds and Their Importance
What type of reactivity is predominant in organic chemistry?
Reactivity is dominated by nucleophilic attack at the carbon atom.
p.7
Coordination Numbers and Geometries
What is the geometry and hybridization of the complex [CoF6]3-?
The geometry is octahedral and the hybridization is sp3d2.
p.16
Magnetic Properties of Complexes
What are the possibilities for d4-d7 systems concerning electron pairing?
For d4-d7 systems, either the electrons can pair in the t2g set (low spin or strong field) or occupy the eg set, higher in energy, without pairing (high spin or weak field).
p.38
Crystal Field Theory and Ligand Field Theory
How can CFSE values help in classifying compounds with the formula AB2O4?
CFSE values can be used to predict whether the compounds belong to normal spinels or inverse spinels.
p.43
Stability of Complex Compounds
Which method is considered the most sensitive and accurate for measuring stability constants?
pH-metry is considered the most sensitive and accurate of all the methods.
p.46
Applications of Coordination Compounds
Why is complex formation important in qualitative methods of analysis?
Complex formation is crucial for the identification and separation of most inorganic ions.
p.5
Coordination Numbers and Geometries
What is the geometry of a tetrahedral copper complex?
Tetrahedral geometry with copper complex having 3d, 4p, and 4s orbitals.
p.15
Crystal Field Theory and Ligand Field Theory
What does the symbol ∆₀ or 10 Dq represent?
It denotes the extent to which the x²-y², z² orbitals and the xy, xz, yz orbitals are split.
p.70
Applications of Coordination Compounds
What is a double salt example mentioned in the text?
Ferric alum (NH4)2SO4.Fe2(SO4)3.24H2O
p.44
Applications of Coordination Compounds
How are coordination compounds utilized in analytical chemistry?
They are used for the extraction of metals and various analytical techniques.
p.59
Organometallic Compounds and Their Importance
What defines an organometallic compound?
An organometallic compound is defined as having a bonding interaction (ionic or covalent) between one or more carbon atoms of an organic group and a metal atom (main group, transition, lanthanide, or actinide).
p.50
Chelating Agents and Their Applications
What are siderophores and provide an example?
Siderophores are naturally occurring compounds used by bacteria to assist in the uptake of iron; an example is desferrioxamine B.
p.59
Organometallic Compounds and Their Importance
Which metalloids are included in the definition of organometallic compounds?
The organic derivatives of boron (B), silicon (Si), germanium (Ge), arsenic (As), and tellurium (Te) are also included under the organometallic definition.
p.19
Spectrochemical Series and Color of Complexes
Rank the following ligands from weaker field to stronger field: I-, Cl-, F-, OH-, H2O, SCN-, NH3, en, NO2-, CN-, CO.
I - < Cl - < F - < OH - < H2O < SCN - < NH3 < en < NO2 - < CN - < CO.
p.16
Crystal Field Theory and Ligand Field Theory
What are the key energy factors mentioned for d4-d7 systems?
Pairing energy (P) and eg-t2g splitting (∆0 or 10 Dq).
p.64
Organometallic Compounds and Their Importance
Who were the Nobel Prize winners in Organometallic Chemistry in 2005?
Schrock, R. H. Grubbs, and Chauvin
p.57
Organometallic Compounds and Their Importance
What is the structure of metal carbonyls?
Metal carbonyls typically feature a central metal atom bonded to one or more carbon monoxide ligands, forming a stable structure characterized by strong metal-ligand interactions.
p.15
Crystal Field Theory and Ligand Field Theory
Which orbitals belong to the E g irreducible representation in the Oh point group?
The x²-y² and z² orbitals belong to the E g irreducible representation.
p.52
Coordination Numbers and Geometries
What complexes are formed during the titration of hard water?
Calcium EDTA and Magnesium EDTA are formed during the titration.
p.43
Stability of Complex Compounds
In which industries are stability constant values of high reliability required?
Stability constant values are required in extraction metallurgy, the nuclear energy industry, analytical methods, and medical, environmental, and industrial research.
p.46
Applications of Coordination Compounds
How can Cd²⁺ ions be detected in the presence of Cu²⁺ ions?
Cd²⁺ ions can be easily detected since only CdS is precipitated when H₂S is passed, despite the presence of more stable Cu.
p.40
Crystal Field Theory and Ligand Field Theory
What limitation does CFT have regarding the relative strengths of ligands?
CFT does not satisfactorily explain the relative strengths of ligands, such as why H2O is a stronger ligand than OH- in the spectrochemical series.
p.45
Applications of Coordination Compounds
What role does zinc play in the extraction of silver?
Zinc is added to the cyanide complex of silver, converting 2 Na[Ag(CN)2] into Na2[Zn(CN)4] and yielding metallic silver.
p.1
Ligands and Their Types
What is a monodentate ligand?
A ligand that forms one bond to a metal ion.
p.69
Organometallic Compounds and Their Importance
What type of bonds are dominant in organic chemistry?
C-C/C-H bonds are covalent.
p.50
Applications of Coordination Compounds
What poisonous gas was used during the First World War?
β-chlorovinyldichloroarsine (Lewisite) was used as a poisonous gas.
p.59
Organometallic Compounds and Their Importance
What is understood about the electropositivity of elements in organometallic chemistry?
In organometallic chemistry, it is understood that the element to which carbon is bound is more electropositive than carbon.
p.12
Crystal Field Theory and Ligand Field Theory
What type of interaction occurs between electrons of the cation and those of ligands in Crystal Field Theory?
The interaction is entirely repulsive, which is responsible for the splitting of d orbitals.
p.34
Coordination Numbers and Geometries
What factors influence the ionic radii of transition metals in complexes?
The ionic radii of transition metals in complexes can be influenced by the oxidation state, the nature of the ligands, and the coordination number.
p.64
Organometallic Compounds and Their Importance
What are the Nobel Prize winners in Organometallic Chemistry for 2010?
Heck, Negishi, and Suzuki
p.53
Coordination Numbers and Geometries
Who proposed Werner's Theory?
Alfred Werner, a Swiss chemist, proposed Werner's Theory.
p.40
Crystal Field Theory and Ligand Field Theory
Why is CFT considered less accurate when covalent bonding increases?
CFT is less accurate because it assumes purely ionic interactions, ignoring the contributions of ligand orbitals and electrons, which become more significant in partially covalent bonds.
p.20
Spectrochemical Series and Color of Complexes
What does increasing CFSE result in?
Increasing CFSE leads to color variations shown with increasing ligand strength.
p.5
Ligands and Their Types
How is the number of d electrons calculated for Cu in CuCl4^2-?
Number of d electrons = Atomic number of central metal - number of electrons lost - Atomic number of previous inert gas. For Cu: 29 - 2 - 18 = d^9.
p.57
Organometallic Compounds and Their Importance
What factors contribute to the stability of metal carbonyls?
The stability of metal carbonyls is influenced by the metal's oxidation state, the nature of the metal-ligand bonds, and steric factors from the ligands attached.
p.23
Magnetic Properties of Complexes
What is the electron configuration of Co3+ in this context?
The electron configuration is d6.
p.44
Applications of Coordination Compounds
What is the biological importance of coordination compounds?
They play significant roles in biological systems, including various biochemical processes.
p.10
Crystal Field Theory and Ligand Field Theory
What do Molecular Orbital Theory and Ligand Field Theory provide, despite being more complicated?
A more realistic perspective on bonding
p.58
Organometallic Compounds and Their Importance
What are organometallic compounds?
Organometallic compounds are generally defined as compounds in which organic groups are linked directly to the metal through at least one carbon atom. Metal hydrides are often included as well.
p.69
Organometallic Compounds and Their Importance
What is the characteristic of the C-X bond in organic compounds?
The C δ+ -X δ- bond is polar (partly ionic).
p.1
Ligands and Their Types
What is a polydentate ligand?
A ligand that can form more than two bonds to a metal ion.
p.23
Charge-Transfer Transitions
What colors do the complexes absorb to favor d-d transitions with strong field ligands?
They absorb violet or blue color.
p.38
Crystal Field Theory and Ligand Field Theory
What does CFSE stand for in the context of predicting the type of spinels?
CFSE stands for Crystal Field Stabilization Energy.
p.9
Magnetic Properties of Complexes
How do magnetic properties of a complex relate to hybridization?
A complex's magnetic properties determine which hybridization is being used, with sp3d2 typically being High Spin and d2sp3 being Low Spin.
p.57
Organometallic Compounds and Their Importance
What are the applications of ferrocene?
Ferrocene is used in fuel additives, as a standard in electrochemistry, and in the synthesis of various organometallic compounds.
p.33
Magnetic Properties of Complexes
How does crystal field splitting affect the magnetic properties of a complex?
Crystal field splitting can lead to either high-spin or low-spin configurations, impacting the number of unpaired electrons and thereby affecting the magnetic behavior of the complex.
p.23
Spectrochemical Series and Color of Complexes
[Co(NH3)6]3+ and [Co(en)3]3+ appear in what color?
They appear orange yellow.
p.28
Crystal Field Theory and Ligand Field Theory
What is the position of four ligands with respect to the d orbitals of the central metal ion in tetrahedral complexes?
The t2 orbitals, which have their lobes oriented in between the axes, are nearer to the four ligands and interact with the ligand orbitals to a greater extent, resulting in higher energy. In contrast, the e orbitals, oriented along the axes, are further away from the ligands and interact to a lesser extent.
p.55
Valence Bond Theory and Hybridization
Who provided the first electronic interpretation of bonding in coordination compounds?
Gilbert N. Lewis in the 1920s.
p.39
Ligands and Their Types
How do ligands influence the formation of outer and inner orbital complexes?
Ligands determine whether a complex is high spin or low spin, influencing the formation of outer or inner orbital complexes.
p.63
Valence Bond Theory and Hybridization
Why is the electronic configuration of carbon considered special?
Carbon can form a full shell with 4 covalent bonds, as the gap between the 2s and 2p orbitals is conducive for bonding without extra electrons or vacant orbitals.
p.39
Magnetic Properties of Complexes
How does Crystal Field Theory interpret the magnetic properties of complexes?
Crystal Field Theory interprets magnetic properties by considering the contributions of orbitals in the context of high spin and low spin configurations.
p.22
Crystal Field Theory and Ligand Field Theory
How does Ligand Field Strength relate to the color of coordination complexes?
The Ligand Field Strength impacts the d-d transition energy, causing different absorption of visible light and resulting in various colors for the complexes.
p.60
Organometallic Compounds and Their Importance
What was Zeise's Salt and when was it discovered?
Zeise's Salt is K + [(C2H4)PtCl3], discovered in 1827.
p.28
Crystal Field Theory and Ligand Field Theory
Why is there a decrease in ∆t when only four ligands are present in tetrahedral complexes?
The presence of only 4 ligands results in a 1/3 decrease in the number of ligands, which decreases the tetrahedral crystal field splitting energy (∆t).
p.27
Coordination Numbers and Geometries
What is the geometry of a tetrahedral complex and how do the ligands occupy the corners of the cube?
In a tetrahedral complex, the ligands occupy four alternate corners of a cube while the metal ion is at the center, leaving the other four corners empty.
p.23
Crystal Field Theory and Ligand Field Theory
What is the effect of strong field ligands on splitting?
They cause more splitting, resulting in a large ∆o.
p.45
Applications of Coordination Compounds
How are silver and gold extracted from their ores?
Silver and gold are extracted through complex formation using cyanide complexes, specifically dicyanoargentite(I) [Ag(CN)2] and dicyanoaurate(I) [Au(CN)2], in the presence of oxygen and water.
p.63
Valence Bond Theory and Hybridization
What is the electronic configuration of carbon?
The electronic configuration of carbon is 1s² 2s² 2p².
p.53
Coordination Numbers and Geometries
What geometries are associated with coordination spheres?
The geometries associated with coordination spheres are square planar and tetrahedral.
p.19
Spectrochemical Series and Color of Complexes
What does the color of a complex depend on for a given ligand?
The color depends on the oxidation state of the metal ion.
p.50
Chelating Agents and Their Applications
What is D-penicillamine used for?
It is used in the treatment for poisoning by heavy metals, including Wilson's disease.
p.29
Crystal Field Theory and Ligand Field Theory
What is the value of ∆o for tetrahedral complexes?
∆o = -0.6 x n(e g) + 0.4 x n(t2g)
p.4
Coordination Numbers and Geometries
What is the coordination number and geometry of the complex [Ni(CN)4]2-?
The coordination number is 4 and the geometry is square planar (dsp2 hybridization).
p.21
Crystal Field Theory and Ligand Field Theory
What causes the splitting of d levels in transition metal complexes?
The d levels in transition elements split into different energy levels depending on the geometry of the complex.
p.61
Organometallic Compounds and Their Importance
What is Zeise's Salt?
The first transition metal organometallic compound isolated by W. C. Zeise by adding potassium chloride to a PtCl4/ethyl alcohol solution.
p.66
Organometallic Compounds and Their Importance
What reaction did Frankland conduct to prepare diethyl zinc?
3 C2H5I + 3 Zn → (C2H5)2Zn + C2H5ZnI + ZnI2
p.50
Applications of Coordination Compounds
How does Lewisite affect the body?
It reacts with the SH groups of various important enzymes.
p.12
Crystal Field Theory and Ligand Field Theory
What happens to the degeneracy of d-orbitals in the presence of ligands according to CFT?
The d-orbitals lose their degeneracy due to the approach of ligands during the formation of a complex.
p.23
Crystal Field Theory and Ligand Field Theory
What is the splitting effect caused by weak field ligands?
They cause less splitting, resulting in a small ∆o.
p.56
Coordination Numbers and Geometries
What is noted as a failure of Sidgwick’s EAN rule?
The Ionic nature of the complexes is noted as a failure.
p.42
Properties of Complex Compounds
What type of electrolytes are complexes considered to be?
Complexes are strong electrolytes.
p.21
Spectrochemical Series and Color of Complexes
What is the general reason why transition metal complexes are colored?
Transition metal complexes are colored due to the promotion of an electron from one energy state to another, which requires energy obtained by absorbing light of a particular wavelength.
p.19
Spectrochemical Series and Color of Complexes
What determines the color of a complex for a given metal ion?
The color depends on the ligand.
p.42
Properties of Complex Compounds
What is primary dissociation in relation to complex ions?
Primary dissociation refers to complexes readily dissociating into a complex ion and a counter ion, such as [Ag(NH3)2]Cl dissociating into [Ag(NH3)2]+ and Cl-.
p.1
Ligands and Their Types
What is a bidentate ligand?
A ligand that forms two bonds to a metal ion.
p.29
Magnetic Properties of Complexes
Why are all tetrahedral complexes considered high spin?
All tetrahedral complexes are high spin since the CFSE is smaller than the pairing energy.
p.44
Applications of Coordination Compounds
In what industrial applications are coordination compounds used?
They are used in a range of industrial processes including catalysis and material synthesis.
p.27
Crystal Field Theory and Ligand Field Theory
Why is the splitting energy (∆t) relatively small in tetrahedral complexes?
The splitting energy (∆t) is relatively small even with strong field ligands because there are fewer ligands to bond with.
p.48
Applications of Coordination Compounds
What are some examples of enzymes that are coordination compounds?
Enzymes like carboxypeptidase A and carbonic anhydrase are examples of biological compounds with coordinated metal ions.
p.60
Organometallic Compounds and Their Importance
Which compound led to a Nobel Prize in 1973?
Ferrocene led to a Nobel Prize in 1973.
p.61
Organometallic Compounds and Their Importance
What happens to Zeise's Salt when kept over concentrated sulfuric acid in vacuo?
It loses water of hydration.
p.10
Crystal Field Theory and Ligand Field Theory
Which theory is known to provide a better understanding of the formation of complexes?
Crystal Field Theory (CFT)
p.28
Crystal Field Theory and Ligand Field Theory
What is the tetrahedral crystal field splitting energy (∆t) in relation to ∆0?
The tetrahedral crystal field splitting energy is given by ∆t = (4/9) ∆0.
p.49
Applications of Coordination Compounds
Which coordination compound is known to effectively inhibit the growth of tumors?
Cisplatin, cis [PtCl2(NH3)2], and related compounds.
p.48
Applications of Coordination Compounds
What is the role of hemoglobin in the blood?
Hemoglobin is the red pigment of blood that acts as an oxygen carrier and is a coordination compound of iron.
p.42
Properties of Complex Compounds
What occurs during secondary dissociation of complex ions?
During secondary dissociation, the formed complex ion may further dissociate, as seen when [Ag(NH3)2]+ dissociates into Ag+ and 2 NH3.
p.51
Applications of Coordination Compounds
What complex ion is formed when AgBr is dissolved in hypo solution during black and white photography?
The complex ion [Ag(S2O3)2]3–.
p.67
Applications of Coordination Compounds
What is one qualitative rule for naming metal/ligand complexes involving Cp ligands?
In formulas with Cp ligands, the Cp usually comes first, followed by the metal center.
p.19
Spectrochemical Series and Color of Complexes
What is the relationship between Δ and λ in the context of ligands?
Larger Δ corresponds to shorter λ, and smaller Δ corresponds to longer λ.
p.4
Coordination Numbers and Geometries
What is the coordination number and geometry of the complex [Co(H2O)6]2+?
The coordination number is 6 and the geometry is octahedral (d2sp3 or sp3d2 hybridization).
p.56
Coordination Numbers and Geometries
How is the Effective Atomic Number (EAN) calculated?
EAN = The sum of the electrons on the central atom + Number of electrons gained or lost in ion formation + Electrons donated from the ligands.
p.27
Magnetic Properties of Complexes
What is the spin state of most tetrahedral complexes and why?
Most tetrahedral complexes are high spin because electrons tend to move up to higher energy orbitals rather than pair up.
p.21
Crystal Field Theory and Ligand Field Theory
What is the relationship between CFSE and the colors of complexes?
Depending upon the Crystal Field Stabilization Energy (CFSE), different wavelengths of light will be absorbed to effect d-d transitions, resulting in complexes having different colors.
p.48
Applications of Coordination Compounds
What diverse functions do metalloproteins with metal ion cofactors perform?
They perform functions including transport, storage, and signal transduction.
p.12
Crystal Field Theory and Ligand Field Theory
How are ligands treated in Crystal Field Theory?
Ligands are considered as point charges.
p.60
Organometallic Compounds and Their Importance
What was probably the first organometallic derivative isolated?
Cacodyl (tetramethyldiarsine) was probably the first organometallic derivative isolated.
p.51
Applications of Coordination Compounds
How are articles electroplated with silver and gold more effectively?
From solutions of the complexes [Ag(CN)2]– and [Au(CN)2]–, which allows for smoother and more even electroplating than from simple metal ions.
p.23
Ligands and Their Types
What type of ligands are NH3, en, and NO2 considered?
They are strong field ligands.
p.67
Ligands and Their Types
How do most authors typically denote a bridging ligand between two metal centers?
Most authors omit x = 2 and just use μ to indicate that the ligand is bridging the simplest case of two metals.
p.56
Coordination Numbers and Geometries
What is Sidgwick’s Effective atomic number (EAN) rule based on?
It is based on the octet theory of Lewis and represents the first attempt to account for bonding in complexes.
p.42
Properties of Complex Compounds
What does the formation constant (Kf) of a complex describe?
The formation constant (Kf) describes the formation of a complex ion from the central metal and the ligands attached to it.
p.58
Organometallic Compounds and Their Importance
Can you name examples of compounds that are not considered organometallic?
Examples include Ti(OC4H9)4, Ca{N(CH3)2}2, and Fe(SC5H11)3.
p.29
Coordination Numbers and Geometries
What geometric configuration is favored in the presence of a very strong ligand?
The square planar geometry will be favored in the presence of a very strong ligand.
p.60
Organometallic Compounds and Their Importance
What are Gilman Reagents and their general formula?
Gilman Reagents are represented by R2Cu – Li.
p.69
Organometallic Compounds and Their Importance
What does 'umpolung' refer to in organometallic chemistry?
C is the negative end of the M-C bond.
p.60
Organometallic Compounds and Their Importance
What is Cacodyl and when was it noted?
Cacodyl, As2(CH3)4, is noted in 1951.
p.61
Organometallic Compounds and Their Importance
What characteristic did Zeise report about the taste of the potassium salt?
He described it as metallic, astringent, and long lasting.
p.58
Organometallic Compounds and Their Importance
What are examples of organometallic compounds mentioned?
Examples include dicobalt(0) octacarbonyl and Zeise’s Salt.
p.22
Applications of Coordination Compounds
What are the colors of various Ni(II) complexes in aqueous solutions starting from NiCl2·6H2O?
[Ni(NH3)6]2+ is pale yellow, [Ni(en)3]2+ is green, [NiCl4]2- is yellow-green, and [Ni(H2O)6]2+ is pink.
p.44
Applications of Coordination Compounds
What medicinal applications do coordination compounds have?
Coordination compounds are used in various medicinal applications, including drug formulation.
p.4
Coordination Numbers and Geometries
What is the coordination number and geometry of the complex [Cr(H2O)6]3+?
The coordination number is 6 and the geometry is octahedral (d2sp3 or sp3d2 hybridization).
p.60
Organometallic Compounds and Their Importance
Who was awarded the Nobel Prize in 1912 for work related to organometallic compounds?
The Nobel Prize in 1912 was awarded for work related to organometallic compounds, including Zeise's Salt.
p.28
Crystal Field Theory and Ligand Field Theory
Why do high energy t2 orbitals have less interaction with ligands in tetrahedral complexes?
Although the high energy t2 orbitals are nearer to the ligands, they do not point directly at the ligands, resulting in less extent of interaction. In contrast, the eg orbitals in octahedral complexes point directly at the ligands.
p.67
Applications of Coordination Compounds
What is the precedence in the listing of hydride ligands in relation to other ligands?
Hydride ligands are sometimes listed first, but rules regarding Cp and other anionic ligands take precedence over this rule.
p.44
Applications of Coordination Compounds
How can coordination compounds be applied in hardness estimation?
They are utilized to estimate the hardness of substances in various analytical methods.
p.69
Organometallic Compounds and Their Importance
What are the types of reactivity observed in organic chemistry?
SN2 and SN1 like reactivity.
p.26
Charge-Transfer Transitions
What are charge-transfer (CT) bands and how do they differ from d-d transitions?
Charge-transfer bands involve the movement of electrons between metal and ligand, similar to d-d transitions, but are often stronger and observed when filled and empty orbitals have similar energies.
p.56
Coordination Numbers and Geometries
What is the EAN for [Ni(CO)4]?
The EAN for [Ni(CO)4] is calculated as 28 - 0 + 8 = 36.
p.27
Crystal Field Theory and Ligand Field Theory
What are the angles between the e and t2 orbitals with respect to the metal and ligand?
The angle between the e orbitals, metal, and ligand is 54° 44', while the angle between the t2 orbitals, metal, and ligand is 35° 16'.
p.23
Charge-Transfer Transitions
What colors do the complexes with weak field ligands absorb?
They absorb yellow or orange.
p.26
Charge-Transfer Transitions
What is Metal-to Ligand Charge Transfer (MLCT) and give an example?
MLCT occurs when charge transfer happens from the metal to the ligand, an example is [Fe(bpy)3]2+ where charge transfer occurs from Fe(II) to the empty π* orbital.
p.21
Ligands and Their Types
How does the nature of the ligand affect the color of transition metal complexes?
The energy difference between split d levels in a transition element depends to a larger extent on the nature of the ligand, affecting the wavelengths of light absorbed and thus the color of the complex.
p.48
Applications of Coordination Compounds
Which coordination compound is known as the anti-pernicious anemia factor?
Vitamin B12, or cyanocobalamine, which is a coordination compound of cobalt.
p.61
Organometallic Compounds and Their Importance
Who discovered Zeise's Salt?
W. C. Zeise, a Danish pharmacist.
p.59
Organometallic Compounds and Their Importance
Do traditional chemists classify metal cyanide complexes as organometallic?
Traditional chemists do not agree on classifying metal cyanide complexes as organometallic.
p.23
Ligands and Their Types
What type of ligands are F- and H2O considered?
They are weak field ligands.
p.58
Organometallic Compounds and Their Importance
Which examples are considered organometallic?
C6H5Ti(OC4H9)3 and (C5H5)2Zr(OOCCH3)2 are considered organometallic.
p.12
Crystal Field Theory and Ligand Field Theory
What is one of the main assumptions of Crystal Field Theory regarding the interaction between metal ions and ligands?
The interaction is purely electrostatic (ionic).
p.26
Charge-Transfer Transitions
What is Ligand to Metal Charge Transfer (LMCT) and when does it occur?
LMCT occurs when charge transfer is favored from the ligand to the metal, often when the metal is in a high oxidation state and attached to π-donor ligands.
p.12
Crystal Field Theory and Ligand Field Theory
What kind of interaction occurs if the ligand is negatively charged according to CFT?
Ion-ion interaction occurs.
p.68
Ligands and Their Types
What do odd η x values usually indicate about carbon ligands?
Odd η x values usually indicate anionic carbon ligands.
p.58
Organometallic Compounds and Their Importance
Who coined the term 'Organometallic'?
The term 'Organometallic' was coined by Edward Frankland.
p.29
Magnetic Properties of Complexes
Are low spin configurations commonly observed in tetrahedral complexes?
Low spin configurations are rarely observed in tetrahedral complexes.
p.70
Ligands and Their Types
What type of bond does the ligand M-N form with the metal in coordination compounds?
A coordinate covalent bond
p.51
Applications of Coordination Compounds
What is Prussian blue and its chemical composition?
A mixture of hexacyanoFe(II) and Fe(III) with the formula Fe4[Fe(CN)6]3, used in inks, blueprinting, and cosmetics.
p.21
Coordination Numbers and Geometries
Why do complexes of s and p block elements appear colorless?
Complexes of s and p block elements are colorless because there are no d-d transitions, as all d levels are doubly occupied, requiring more energy to promote electrons, typically in the UV region.
p.61
Organometallic Compounds and Their Importance
What happens to Zeise's Salt when exposed to air and light?
It gradually becomes covered with a black crust.
p.48
Ligands and Their Types
What is Heme B and its significance in relation to metal coordination?
Heme B is a porphyrin that binds iron and is an example of a biomolecule containing non-protein ligands for a transition metal.
p.56
Coordination Numbers and Geometries
What is the EAN calculation for [Fe(CN)6]4-?
The calculation is 26 - 2 + 12 = 36.
p.26
Charge-Transfer Transitions
Can you give an example of LMCT?
An example of LMCT is found in MnO4-, where the color is due to charge transfer from O2- to Mn(VII), described as an LMCT band.
p.51
Applications of Coordination Compounds
Who accidentally created Prussian blue and when?
The colormaker Diesbach of Berlin in about 1704 during experiments with the oxidation of iron.
p.22
Charge-Transfer Transitions
What happens during d-d transitions in coordination compounds?
d-d transitions occur through the absorption of visible radiation by transition metal ions, resulting in the transmitted light exhibiting the complementary color of the absorbed light.
p.27
Crystal Field Theory and Ligand Field Theory
Why do t2 orbitals have higher energy compared to e orbitals in tetrahedral complexes?
The t2 orbitals have higher energy compared to e orbitals because they are closer to the direction of the ligand approach.
p.12
Crystal Field Theory and Ligand Field Theory
What type of interaction occurs if the ligand is neutral in Crystal Field Theory?
Ion-dipole interaction occurs.
p.12
Crystal Field Theory and Ligand Field Theory
Where do electrons on metal occupy in relation to the ligands during the approach?
Electrons on metal occupy those d-orbitals farthest away from the direction of approach.
p.12
Crystal Field Theory and Ligand Field Theory
Does Crystal Field Theory consider the overlapping between metal and ligand orbitals?
No, CFT does not consider the overlapping between metal and ligand orbitals.
p.42
Properties of Complex Compounds
How are stepwise stability constants and overall stability constants related?
Stepwise stability constants (Kn) and overall stability constants (βn) are related such that βn = K1 K2 K3 K4 ... K n.
p.50
Chelating Agents and Their Applications
What is British Anti-Lewisite (BAL) and its function?
BAL (2,3-dimercaptopropanol) forms a stronger complex with arsenic and acts as an antidote.
p.67
Ligands and Their Types
How are bridging ligands typically positioned in a chemical formula?
Bridging ligands are usually placed next to the metals they bridge, followed by other ligands.
p.26
Charge-Transfer Transitions
What determines the direction of electron transfer in charge-transfer transitions?
The direction of electron transfer is determined by the relative energy levels of the ligand and metal orbitals.
p.68
Ligands and Their Types
What does the symbol η x represent in ligand nomenclature?
The symbol η x indicates how many carbons of a π-system are coordinated to a metal center.
p.68
Ligands and Their Types
What is hapticity in the context of ligands?
Hapticity describes the bonding mode of a ligand to a metal center.
p.56
Coordination Numbers and Geometries
What is the EAN for [Zn(NH3)4]2+?
The EAN is calculated as 30 - 2 + 8 = 36.
p.60
Organometallic Compounds and Their Importance
What are Grignard Reagents represented by?
Grignard Reagents are represented by RMgX.
p.58
Organometallic Compounds and Their Importance
What is the relationship between organometallic chemistry and coordination chemistry?
Organometallic chemistry is a branch of coordination chemistry where the complex has one or more metal-carbon bonds.
p.69
Organometallic Compounds and Their Importance
What types of substitution reactions occur at the metal in organometallic compounds?
Associative and dissociative substitution at M.
p.56
Coordination Numbers and Geometries
What is the EAN for [V(CO)6]-?
The EAN calculation is 23 + 1 + 12 = 36.
p.19
Spectrochemical Series and Color of Complexes
Which complex shows a shift in color due to the ligand in cobalt (III) complexes?
Complexes of cobalt (III) show a shift in color due to the ligand.
p.27
Coordination Numbers and Geometries
What is the orientation of the e and t2 orbitals in a tetrahedral complex?
In a tetrahedral complex, the two e orbitals point to the center of the cube faces while the three t2 orbitals point towards the edges of the cube.
p.69
Organometallic Compounds and Their Importance
How does reactivity differ in organometallic chemistry compared to organic chemistry?
Reactivity is dominated by nucleophilic attack on the metal atom and electrophilic attack on the carbon atom.
p.56
Coordination Numbers and Geometries
What are some exceptions to Sidgwick’s EAN rule?
[Fe(CN)6]3- and [Co(NH3)6]2+ are noted as exceptions.
p.68
Ligands and Their Types
How many electrons are donated by a neutral ligand in the even case?
In the even case, the number of electrons donated by the ligand is usually equal to x.
p.68
Ligands and Their Types
What does an η 5-cyclopentadienyl ligand indicate?
An η 5-cyclopentadienyl ligand indicates that all five carbons of the ring are bonding to the transition metal center.
p.68
Ligands and Their Types
What do even η x values usually indicate about carbon π-system ligands?
Even η x values usually indicate neutral carbon π-system ligands.
p.60
Organometallic Compounds and Their Importance
What was the first transition metal organometallic compound?
The first transition metal organometallic compound was related to Zeise's Salt.
p.12
Crystal Field Theory and Ligand Field Theory
How do electrons on the metal behave in relation to the electrons on the ligands in CFT?
Electrons on the metal are under repulsion from those on the ligands.
p.68
Ligands and Their Types
How is the number of electrons donated by a ligand calculated in the ionic method?
The number of electrons donated by the ligand is usually equal to x + 1.
