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The document is an examination paper for Inorganic Chemistry focusing on Organometallic Chemistry, with a total of 75 marks. It includes various questions on topics such as oxidative addition, reductive elimination, migratory insertion, and the mechanisms of different organometallic reactions. Students are required to attempt all questions, and the paper emphasizes understanding of reaction mechanisms and applications in catalysis.

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86 views

omc previous question

The document is an examination paper for Inorganic Chemistry focusing on Organometallic Chemistry, with a total of 75 marks. It includes various questions on topics such as oxidative addition, reductive elimination, migratory insertion, and the mechanisms of different organometallic reactions. Students are required to attempt all questions, and the paper emphasizes understanding of reaction mechanisms and applications in catalysis.

Uploaded by

iram nabi
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
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Roll No., McH -403 sc. Chemistry (Semester IV) End Semester Examination, 2024 Inorganic Chemistry Paper ~ XX! Organometallic Chemistry Time: 03 Hours ‘Maximum Marks: 60 seipt of this question paper) “Attempt any five questions, sber on the top immediately on rec ‘All questions carry equal marks (write your roll num Question NO. 1 is compulsory. S.No. ‘Marks 02 ai.(a) “Write the product and the type of mechanism in the following reactions. Also write the electron count and formal oxidation stat product. i vi te of the metal in the reactant and the | each Q2.(a) (b) {) 7 7 G e Fe ee ‘when measured at room temperature indicated IR spectra bands at em, 1961cm?, 1795cm+ and when re a reaches at high tem| (b) | two electron electrochemical reduction of the 18-electron cation {(n*-indenyl)2 {co} is reversible while the same reduction of the complex [Cp2V(CO)a]*leads | 4 to the cleavage of a molecule of CO. Explain giving reasons. Explain the stereochemical non-rgidty in organometallic complexes (c) | differentiating the Berry pseudo-rotation and fluxionality with suitable examples, 03 Q7 | Explain following (Any three): a (a) | Oxidative Coupling am (b) | Modes of bonding in alkylidene complexes (c)_| Compulsion to follow the 18-electron rule in reference to carbonyl compl 4{d)_| Role of solvent in reductive elimination reactions plexes ‘organometallic complexes in refe (e) Importance of orgs pl erence to metathesis reaction, @ scanned with OKEN Scanner Your Roll No- aSc. Chemistry IV Semester Examination 2015 Inorganic Chemistry Paper ~- XVII ‘Organometallic Chemistry ‘rime: Three Hours Maximum Marks: 75 ately on the receipt of this question PaPSr Write your Roll No on the top immedi Answer all questions. All questions carr equal marks qi Explain the stereo-chemical_ non-rigidity in organometalic complexes 05 each differentiatins i in Berry Pseudo-rotation and Fluxionality with suitable examples bb. At ambient temperature the proton NMR of CpRh(CzHa)z in CHC shows three peaks: ‘« 5.15 ppm (6)doublet corres ‘5 2.27ppm (6) 4(H) and 1.12pem (5) ‘onding to the Cp protons (ai) both corresponding to ether protons © At -20% resonances at 2.27 & 1.12 to be split into two Pi — doublets. While heating to 57°C the et sthylene protons resonate stion enerey for the process is 6.2 keal/mol © scanned with OKEN Scanner Q3 aa . What are ‘De-insertion reactions’. Explain detailed mechanism. (COOH), ecocl CFA snCly Hy . Explain the difference in the Migration and Insertion reaction? Write 08 general features of Migratory Insertion (MI) reactions. 0) ove’ 2 Explain the role of solvent in ‘Reductive Elimination Reactions (RER)’. 05 eay wo How will you prove that the departing groups in the RER are ‘Cis’ t eS each other? \ 2 Wik the differences in the Fischer and Schrock’s Carben oe e ic applications of organo, 7 met ; allic complexes? 5 “ Explain OS eah® ~( \ 2 AzM, @ scanned with OKEN Scanner Your Roll No. cH-403 MSc. Chemistry, IVth Semester Examination, 2012 Inorganic Chemistry Paper No. XVII Organometallic Chemistry - Il Maximum Marks: 75 ime: Three Hours 7 rite your Roll no. on the top immediately on receipt of this question paper.) itcdo: Attempt all questions. Marks are given in the right hand margin. at, (@) Wite the structure of Ziegler —Natta catalyst ‘Show its importance in stereo- specific polymerization of monomers. 7 (b) Discuss in brief the nucleophilic and electrophilic reactions of co-ordinated 8 complexes. 2. (@) Write any two for co-ordinated ligand complexes: () Cyclization reaction (ji) Ring expansion reaction (iii) Transmetallation reaction. reaction in d° complexes. 7 oxidative addition reaction, justify 3 (b) What are Oxidative Addition Reactions? Show the (6) Which among the following will not undergo your answer? () _Ir(PPhs)2(CO)CI (i). [Rhl(CO)2]~ (i) [Cp2TiMect)~ 03, {@) Discuss the types of metal carbenes. List in detail about the synthesis and requisites for ‘Fisher Carbene’. Write an evidence to prove that Fisher Carbene is Electrophilic in nature. 9 (b) Write the mechanism for ‘Wacker-Schmidt reaction’ and show its industrial importance. 6 1/2 @ scanned with OKEN Scanner FF Q4. (a) Whats ‘Fluxionality’? Explain the term in ‘pi olefin Complexes’. 6 (b) Write a mechanism for the Palladium catalysed oxidation of alkenes ang mark the steps, 6 (c) Write mechanism for ‘Synthesis —Gas’ formation. 4 5. (@) Write “the mechanism of following using organometallic compounds ‘Water ~gas shift’ or Hydroformylation reaction. 6 (b) Explain Reductive Elimination reaction? Write the elimination product in each of the following which is least likely to undergo RE. Also write the oxidation — humber of the metal ion in the reactant as well as product. 3+6 7 Cc N © scanned with OKEN Scanner Roll No... cH-403, ‘ M.Sc. Chemistry IV Semester Examination 2013 Inorganic Chemistry Paper — XVII (i) Organometallic Chemistry Time: Three Hours Maximum Marks: 75 Write your Roll No on the top immediately on the receipt of this question paper. ‘Answer all questions. All questions carry equal marks 1. Explain the following for organometallic complexes, giving examples: (5x3=15) i. Cyclization reaction |. Transmetallation reaction Nucleophilic attack iv. Migration reaction v. Insertion reaction iving the mechanism. 2,(a) What are Oxo processes? Explain gi for Mosanto acetic (b) What is heterogeneous catalysis? Write the mechani: acid cycle and mark the steps involved. (c) Write the mechanism for hydrformylation reaction. ‘OR the Fluxionality in butadiene—Fe(CO); complex on the basis of its: 3C NMR data ji, activation energy data i (b) support your explanation with absorption data for the changes observed in © poton NMR spectrum of CpRh (CoH)2 in CHCl3: ji, onambient temperature. “ii, when the same solution is cooled to -20°C. @ scanned with OKEN Scanner OR ne he oxidative addon reactions{OAR) andiist the essential crite, (a) Define for OAR. the nature of prod {b) Write the variation in mechanism of OAR and Product, when the ‘ incoming ligand X-¥ is: ; i. polar ii, non-polar 44, Write the mechanism for the following in organometallic complexes: (eax {a) Ring expansion reaction (b) Electrophilic reaction (c) Ligand exchange reaction OR (a) What are Migratory insertion reactions? Explain its mechanism, fr (b) What are de-insertion reactions. Write its mechanism, ( ; 5) 5. What are elimination reactions? Explai plain the ing i i aie, Riicio one following in detail with mechanism: (5) (b)B-hydride eliminatic lon/ transfer reaction @ scanned with OKEN Scanner ce) Your Roll No. M.Sc. Chemistry/ IV Semester Examination 2014 Inorganic Chemistry v Paper -- XVII (ii) Organometallic Chemistry Time: Three Hours Maximum Marks: 75 ‘Write your Roll No on the top immediately on the receipt of this question paper. Answer all questions. All questions carry equal marks Q1 a) Against each statement mark.the appropriate type of reaction/s from 01 each the oxidative addition, reductive elimination, migratory insertion and B- H transfer:- |. Cis orientation of the participating ligand/s is a must fi, This reaction does not occur for d” metal complexes: This reaction is enthalpy favoured and entropy prohibited iv. Avacant coordination site on the metal centre is prerequisite v. There is an increase in the electron count of the metal complex » by two units during this reaction b) Which statements given below describe a Fischer or Schrock type of 01 carbene ¥ ; i, It behaves like a phosphorous ylide in some of its reactions The carbene carbon is nucleophile in nature It is synthesized from metal carbonyl precursors @ scanned with OKEN Scanner Q2 a) b) a) b) Q3 at room temperature the signal broadens and then separates ions Explain the above observatior terms Fluxionality and Tautomerism. Explain pifferentiate between th ity with special reference to five the stereo-chemical non "16! coordinate complexes. uplan the scrambling of carbonyls, groups in metal carbonyls in reference to— i. Polytopal rearrangements inter-conversion of bridging and terminal rearrangements oR Explain the scrambling of carbonyl groups in the following complexes with the help of their “C NMR data. i. [CpaFe(CO), Jand ii. (CpRn(CO)}s What do you mean by ‘Ring Whizzing’? Elucidate the structure of [(n'cp) (n°Cp}Fe(CO).] on the basis of variable ternperature "H NMR studies, ‘What is the di i. difference between the oxidative addition reaction (OAR) and oxidative coupl _— Pling reactions? Explain in detail the OAR for d® and d’ ing the concerted, , ni — jon concerted and free radical OR What are the reductive eliminatic criterion they follow to Occur? He (0 roups in RE reactions are Cis to ea ion Feactions (RE) and the general Ww will ye YOU prove that the departing ich other? a @ scanned with OKEN Scanner 0 08, 10 05 15 a4 Qs Explain the ‘Intramolecular insertion reactions’ and their general 45 features. Discuss the mechanism of insertion of an alkene to a metal complex. OR Define metal carbenes and their types comparing their properties and chemical behaviour on the basis of metal-carbene bonding. Write the mechanism of foliowing reactions and mark each step 7.5 involved, quoting their socio-economic importance : {any two) a) Hydroformylation b) Polymerization of alkenes ©) Hydrogenation of alkenes d) Monsanto acetic acid reaction @ scanned with OKEN Scanner CH-483 (SET—B) Roll No. M.Sc. (Final) Chemistry, Annual Examination ~ 2011 Inorganic Chemistry Paper No Vil (Organometallic Chemistry) Time: Three Hours Maximum Marks: 75 NOTE: Attempt any five. All question carry equal marks 14 @ rte down the hydrogenation process of alkenes, Show the steps involved and marked the electron count and type of reaction at each step. (08) o ‘What is Isomerisation process. Give a suitable mechanism for the same. (07) 2 (@) Write the structure of Zeiglar -Natta catalyst. Show its importance in stereo- specific polymerization of monomers. (08) (6) Write @ mechanism for the Palladium catalysed oxidation of alkenes and mark the steps invohed. (07) 3. (@)__ Explain the classification of organometalic compounds based on the ‘HAPTICITY" and the polatty of Metal-carbon bond with examples and state the general rules followed for the nomenclature of pi ‘complexes. (09) (b) Give the synthesis of organometallic pi complexes by following methods (any three) with examples — Redistribution method, sigma-pi rearrangement, Aditon reaction, or Cyclization (06) 4, Brief about Vibrational-Rotational spectroscopy and its applications in following — (@) Effect of complex formation on the symmetry of ligands (special reference to carbonate and sulphate co-ordination) (06) (0) Effect of complex formation on the electronic stricture and bonding characteristics of ligand (special reference to N-H, C-N and C-O bonds} (09) 5. (2) __wite the following reactions for metal cerbonyl complexes in view of 18 electron rule — substitution, oxidation and reduction reactions (09) (b) _ Onthe basis of IR spectroscopy make a distinction between the stretching frequencies in the ‘erminal and bridging CO in the metal carbonyl complex with example : 6 —(@) __Compare the following mechanism for cyclopentadieny and arene pi complexes “Friedal-Craft Acylation or Addition reactions and ligand or metal exchange reaction 6) Write down the Flusionalty and relate it with Dynamic Equaliria in pi olefin ‘organometallic complexes. é ‘Wirt the mechanism of (any three) of following for organometalic compounds ~ clrophicaltack of co-ordinated ligands @ scanned with OKEN Scanner M.Sc. (Sem — IV) Chemistry ~ 2011-12 Paper No XVII (i), (Organometallic Chemistry) Time: Three Hours ‘Maximum Marks: 75 NOTE: Attempt all questions. All questions carry equal marks ee Q1| A Write the structure of Ziegler -Natta catalyst. Show its 10 importance in stereo- specific polymerization of monomers B. Write the nucleophilic attack reaction in brief for co- 05 ordinated complexes. Write any two for co-ordinated ligand complexes— e — Cyclization reaction e Ring expansion ¢ — Transmetallation reaction What ate Oxidative Addition Reactions? Show the reaction in d? complexes in detail. Which among the following will not undergo O A R, give reasons? © Ir(PPHs)2COCI e — Rhi(CO)} © 1 Cp2TiMeCll ~ Discuss the types of metal carbenes. List in detail about the synthesis and requisites for ‘Fisher Carbene’. Write an evidence to prove that Fisher Carbene is Electrophi in nature. . Write the show its industri @ scanned with OKEN Scanner a3) Q4 . What is ‘Fluxionality'’? Explain the term in ‘pi olefin . Write mechanism for Synthesis -Gas formation Sa ar eee A. Discuss the types of metal carbenes, List in detail about| 02 the synthesis and requisites for ‘Fisher Carbene’. Write +03 an evidence to prove that Fisher Carbene is Electrophile | +02 in nature. +02 Write the mechanism for ‘Wacker- Schmidt reaction’ and show its industrial importance. 96 Complexes’ Write a mechanism for the Palladium catalysed oxidation of alkenes and mark the steps Q5 . Write the mechanism of following for organometallic . Explain Reductive Elimination reaction? writ compounds -- Water -gas shift or Hydroformylatior reaction elimination product in each of the following which j likely to undergo RE. Also write the oxidatio the metal ion in the reactant as well as p @ scanned with OKEN Scanner a4] A. What is ‘Fluxionalit (Saiga Ikram) Assistant Professor y? Explain the term in ‘pi olefin) 05 — Complexes’ | |B. Write a mechanism for the Palladium catalysed oxidation 06 | of alkenes and mark the steps | C. Write mechanism for Synthesis -Gas formation 04 | | | | vA 6 Write the mechanism of following for organometallic compounds -- Water -gas shift or Hydroformylation reaction Explain Reductive Elimination reaction? Write the elimination product in each of the following which is least] likely to undergo R E. Also write the oxidation num the metal ion in the reactant as well as product @ scanned with OKEN Scanner cH-483 | M.Sc. (Final) Chemistry - 2012 (Annual Scheme) Paper No Vill, (Organometallic Chemistry) Time: Three Hours Maximum Marks: 75 NOTE: Attempt any five. All question carry equal marks Qi] a Explain the classification of organometallic compounds based the ‘HAPTICITY” and the polarity of Metal-carbon bond with examples and state the general rules followed for the nomenclature of pi complexes Give the synthesis of organometallic pi complexes by following | 06 methods (any three) with examples. Redistribution method, sigma-pi rearrangement, Addition reaction, or Cyclization Q2 |. write the following reactions for metal carbonyl complexes in view | 09 of 18 electron rule —substitution, oxidation and reduction reactions . On the basis of IR spectroscopy make a distinction between the | 06 stretching frequencies in the terminal and bridging CO in the metal carbonyl complex with example. (06) Q3 a. Distinguish the preparation of transition metal carbonyl complexes | 06 by using suitable reducing agent and carbonyl (CO) itself as - ea tli : reducing agent . Describe the following reactions in metal carbonyl complexes in | 09 detail (i) Substitution reactions, (li) oxidation reactions, (iii) Lewis base behaviour a4 Write the mechanism of (any three) of following for organometallic (05 compounds -- each) (a) Electrophilic attack of co-ordinated ligands (b) Water -gas shift (c) Hydroformylation (d) Insertion-elimination 1. Write the structure of Zeiglar -Natta catalyst. Show its imy in stereo- specific polymerization of monomers. . State and explain co-oligopolymerization . Write a mechanism for the Palladium catalysed oxid alkenes and mark the steps involved with the electron each intermediate formed during the process, @ scanned with OKEN Scanner Q7 | 2. Compare the following mechanism for cyclopentadienyl and arene | (08) pi complexes Friedal-Craft Acylation or Addition reactions and ligand or metal ‘exchange reaction b. Write down the Fluxionality and relate it with Dynamic Equalibria in | (07) pi olefinic and pi allylic organometallic complexes. @ scanned with OKEN Scanner cy 6ET-A) Roll No, MSc. (Final) Chemistry, Annual Examination ~ 2014 Inorganic Chemistry Paper No Vill (Organometallic Chemistry) Time: Three Hours Maximum Marks: 75 NOTE: Attempt any five. All question carry equal marks (@ Explain the classification of organometallic compounds based on the type of organic “pi” ligands with examples and state the general rules followed for the nomenclature of pi complexes. (09) () Give the synthesis of organometallic pi complexes by following methods (any three) with examples Direct synthesis, Redistribution method, sigma-pi rearrangement, Addition reaction, Ccization or Substitution method (08) 2 @ Compare the following mechanism for cyclopentadienyl and arene pi complexes Friedal-Craft Acylation or Addition reactions and ligand or metal exchange reaction (08) (0) Write down the Fluxionalty and relate it with Dynamic Equalibria in pi olefinic and pi allylic ‘oiganometalic complexes, (7) 3. (@)__Distinguish the preparation of transition metal carbonyl complexes. by using suitable reducing agent and carbonyl (CO) itself as reducing agent (08) (0) Describe the folowing reactions in metal carbonyl complexes in detail (i) Substitution reactions, (ii) oxidation reactions, (i) Lewis base behaviour (09) ; 4. On account of infra-red spectroscopy explain (any three) in coordination complexes —- (05 each) (2) Identification of inorganic ions and halogens (&) Shape and symmetry of molecules (@) Effect of mass ofthe atom and neighbouring group (d) Effect of dference in elecro-negatity and Hydrogen bonding @ Show the steps involved and marked the electron count and type of reaction at each step, (6) Using only the migration of double bond in alkene give a suitable mechanism for the produ propionaldehyde from ally alcohol. (@) Wacker- oxidation (b) Mosanto acetic acid preparation (9) Hydrotormyation @ scanned with OKEN Scanner nat) 499 925800 3 M.Sc. (Final) Chemistry - 2011 Paper No Vil, (Organometalic Chemisty) Time: One & half Hours Maximum Marks ore: tempt any three. All question cary equal marks 1. (@)__ Explain the classification of organometallic compounds based on the ‘HAPTICITY” and the polarity of Meta-carbon bond with exam; | ples and state the general rules followed for the nomenciature of pi complexes. (03) () Give the synthesis of organometalic pi complexes by following methods (any three) with examples.~ Redistribution method, sigma-pi rearrangement, Addition reaction, or Cyclization (06) 2, ((@)___ write the following reactions for metal carbonyl complexes in view of 18 eleotron rule — substitution, oxidation and reduction reactions (09) (b) On the basis of IR spectroscopy make a distinction between the stretching frequencies in the terminal and bridging CO inthe metal carbonyl complex nih examie (06) OR (2)__ Distinguish the preparation of transition metal carbonyl complexes by using suitable reducing agent and carbonyl (CO) itself as reducing agent (06) (b)___ Describe the folowing reactions in metal carbonyl complexes in detail () Substitution reactions, (i) oxidation reactions, (i Lewis base behaviour (08) 4, Write the mechanism of (any three) of following for organometalic compounds — (05 each) (2) Electrophiic attack of co-ordinated ligands (b) Water -gas shift (6). Hydroformylation (@) Inserton-elimination 5. (@) Write the structure of Zeiglar -Natta catalyst. Show its importance in stereo- specific polymerization of monomers. (08) (b) Write @ mechanism for the Palladium catalysed oxidation of alkenes and mark the steps involved, (07) (H.483 (Sessional 1) Msc. Final) Chemistry ~2011 Paper No Vil, Organometalc Chemistry) Time: One & half Hours Maximum Marks ‘Attempt any three. All question carry equal marks 1. (@) Explain the classification of organometalic compounds based on the 'HAPTICITY" and the polarity of Metal-carbon bond with examples and state the general rules followed for the nomenclature of pi complexes. 09) (0) Give the synthesis of organometalc pi complexes by following methods (any three) with examples Redistribution method, sigma-i rearrangement, Adon reacon, or Cyclization (06) 2 (2) wiite the following reactions for metal carbonyl complexes in view of 18 electron rule substitution, oxidation and reduction reactions (09) (b) On the basis of IR spectroscopy make a distinction between the stretching frequencies in the ‘emia and ring CO in he metal carton complex wih example ite) 5. (@) Distinguish the preparation of ranstion metal carbonyl complexes by using suitable reducing ‘gent and carbony| (CO) itself as reducing agent ‘asp () scribe the following reactions in metal cerbonyl complexes in detail thovtetaoe Teadtons, i) oxaon reactions, i) Levis base behaviour (09) 8. Write the mechanism of (any three) of following for organometalic compounds ~ (05 each) (e) Elecrophiic attack of co-ordinated ligands () Water -gas shift (g)_Hydroformylation a vo tee of Zelglar -Natia catalyst. Show its importance in stereo- specie F ; Be (08) eee seria tae for the Palladium catalysed oxidation of alkenes and mark the steps involved, 7 @ scanned with OKEN Scanner

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