Derive general rate law, organometallic (That's all the info, nothing else) Consider an 18-electron complex (diene) Cr(CO)4. Reaction with a ligand L (such as a phosphine, for example) generally results in complete displacement of the diene ligand to give Cr(CO)4L2; the plausible intermediate where a single L has been added and only one of the diene double bonds remains coordinated reacts much too rapidly with additional L to be isolated (or even observed). Formation of that intermediate could in principle proceed via either a dissociative mechanism or an interchange mechanism. Assuming that both mechanisms operate, use the steady-state approximation to derive the general rate law for the reaction, and sketch what a plot of rate vs. [L] would look like. Then show how the rate law would simplify if only one of the two alternative mechanisms were significant and sketch the corresponding rate vs. [L] plots for each of those cases. OC OC CO DCr(CO)4 OC PEt3 PEt3 OC PEt3 Cr(CO)4L2 CO CO OC. OC major intermediates: OC OC PEt3 CO CO D*Cr(CO)4 D*Cr(CO)4L

Derive general rate law, organometallic (That's all the info, nothing else) Consider an 18-electron complex (diene) Cr(CO)4. Reaction with a ligand L (such as a phosphine, for example) generally results in complete displacement of the diene ligand to give Cr(CO)4L2; the plausible intermediate where a single L has been added and only one of the diene double bonds remains coordinated reacts much too rapidly with additional L to be isolated (or even observed). Formation of that intermediate could in principle proceed via either a dissociative mechanism or an interchange mechanism. Assuming that both mechanisms operate, use the steady-state approximation to derive the general rate law for the reaction, and sketch what a plot of rate vs. [L] would look like. Then show how the rate law would simplify if only one of the two alternative mechanisms were significant and sketch the corresponding rate vs. [L] plots for each of those cases. OC OC CO DCr(CO)4 OC PEt3 PEt3 OC PEt3 Cr(CO)4L2 CO CO OC. OC major intermediates: OC OC PEt3 CO CO DCr(CO)4 DCr(CO)4L

Chemistry

10th Edition

ISBN:9781305957404

Author:Steven S. Zumdahl, Susan A. Zumdahl, Donald J. DeCoste

Publisher:Steven S. Zumdahl, Susan A. Zumdahl, Donald J. DeCoste

Chapter21: Transition Metals And Coordination Chemistry

Section: Chapter Questions

Problem 108IP: a. In the absorption spectrum of the complex ion Cr(NCS)63, there is a band corresponding to the...

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a. In the absorption spectrum of the complex ion Cr(NCS)63, there is a band corresponding to the absorption of a photon of light with an energy of 1.75 104 cm-1. Given 1 cm1 = 1.986 1023 J, what is the wavelength of this photon? b. The CrNC bond angle in Cr(NCS)63 is predicted to be 180. What is the hybridization of the N atom in the Ncs- ligand when a Lewis acid-base reaction occurs between Cr3+ and NCs- that would give a 180 CrNC bond angle? Cr(NCS)63 undergoes substitution by ethylenediamine (en) according to the equation Cr(NCS)63+2enCr(NCS)2(en)2++4NCS Does Cr(NCS)2(en)2+ exhibit geometric isomerism? Does Cr(NCS)2(en)2+ exhibit optical isomerism?
Four different octahedral chromium coordination compounds exist that all have the same oxidation state for chromium and have H2O and Cl as the ligands and counterions. When 1 mole of each of the four compounds is dissolved in water, how many moles of silver chloride will precipitate upon addition of excess AgNO3?
Trimethylphosphine, P(CH3)3, can act as a ligand by donating the lone pair of electrons on the phosphorus atom. If trimethylphosphine is added to a solution of nickel(Il) chloride in acetone, a blue compound that has a molecular mass of approximately 270 g and contains 21.5% Ni, 26.0% Cl, and 52.5% P(CH3)3 can be isolated. This blue compound does not have any isomeric forms. What are the geometry and molecular formula of the blue compound?
The square-planar complex Pt(en)Cl2 has chloride ligands in a cis configuration. No trans isomer is known. Based on the bond lengths and bond angles of carbon and nitrogen in the ethylenediamine ligand, explain why the trans compound is not possible.
Which of the following statement(s) is( are) true? a. The coordination number of a metal ion in an octahedral complex ion is 8. b. All tetrahedral complex ions are low-spin. c. The formula for triaquatrianuninechromiwn(III) sulfate is [Cr(H2O)3(NH3)](SO4)3. d. The electron configuration of Hf2+ is [Xe]4f126s2. e. Hemoglobin contains Fe3+.
Classify each ligand as monodentate, bidentate, and so on. (a) (CH3)3P (b) H2N(CH2)2NH(CH2)2NH2 (c) H2O
3. Reaction of [(CH2=CH2)2RHCI]2 (A) with two equivalents of a phosphine ligand under nitrogen results in displacement of ethylene by phosphine. With triethylphosphine, the reaction yields a dimer, [RhCl(PET3)2]2.(B). With 'Pr°P, a monomeric N2 complex is formed, RHCI(N2)(P'Pr3)2].(C). Draw structures of A, B and C. Explain why different results are seen with the two different phosphines.
Which complex below is an organometallic complex? O [Pd(acac)2] O [PdCl2(PME3)2] O [Pd(OH)2(H20)2] O [PDH2(PME3)2]
(c) Explain which one of each of ´the following pair of clectronic transitions should be mcre intensed: ( 'Ag→T20, in [CoClj3- or 'A->'Tz in (Co(bpy)3] 3+ (ii) 'A, (Ru)→'E (Ru) or (T* of ligand in [Ru(bpy)3]²*) 'A, (Ru)→'s MLCT.
2. When an anhydrous solution of CrCl₂ in EtOH was treated with ligand 1 (below), a precipitate of complex X appeared, and this was filtered off under an atmosphere of nitrogen. A sample of 'hydrated chromium(III) chloride' (actually, [CrCl2(H2O)4]Cl-2H2O) was dissolved in dimethylformamide and boiled (153 °C) to remove water. To the resulting purple solution was added an excess of ligand 1 (below) at 130 °C. On allowing the mixture to cool, a precipitate appeared, complex Y. Analytical and magnetic data for X and Y are given below. Complex X N NH2 1 Complex Y Found: % C=42.4, H = 4.8, N = 16.5, Cl Found: % C = 38.4, H = 4.4, CI = 28.5, = 21.0, Cr 15.5 = Magnetic moment = 4.9 μB Cr = 13.9. Magnetic moment = 3.87 MB a. Explain all the analytical data and the information in the description above, hence deduce possible structures for X and Y. Explain your reasoning. b. What is the likely geometry of the anionic ligands for complex X? Explain your reasoning. C. How many geometric isomers…
3 You have a neutral, 4-coordinate macrocyclic ligand that binds to Ni(II). When a weakly-coordinating perchlorate ion (CIO4-2) is the anion in solution, it produces a red-colored diamagnetic low-spin d8 complex. When perchlorate is replaced by two thiocyanate ions, (SCN-), the Ni-macrocycle complex turns violet and has two unpaired electrons. Predict what has happened to the geometry and the d-orbital splitting that has resulted in the change in color?
Consider the following reaction: [Cr(H2O)5(SCN)]2+ + Yn- --> [Cr(H2O)5Y](3-n)+ + SCN- Which statement is true if this reaction occurs via a dissociation mechanism? Group of answer choices Changing the incoming ligand, Yn-, will have a large effect on the rate constant. The first step of the mechanism is the addition of the Yn- ligand to form a 7-ccordinate intermediate, [Cr(H2O)5(SCN)Y](2-n)+ Changing the incoming ligand, Yn-, will have very little effect on the rate constant. It is impossible for this reaction to occur via a dissociation mechanism.