Inorganic Chemistry: Some New Facets

664 Pages·2021·7.312 MB·English

by  Ram Charitra Maurya

RamCharitraMaurya
InorganicChemistry
Also of Interest
BioinorganicChemistry.
PhysiologicalFacets
RamCharitraMaurya,
ISBN----,e-ISBN----
MolecularSymmetryandGroupTheory.
ApproachesinSpectroscopyandChemicalReactions
R.C.Maurya,J.M.Mir,
ISBN----,e-ISBN----
ChemistryoftheNon-Metals
RalfSteudel,
ISBN----,e-ISBN----
OrganoseleniumChemistry
BrindabanC.Ranu,BubunBanerjee(Eds.),
ISBN----,e-ISBN----
Ram Charitra Maurya
Inorganic
Chemistry
Some New Facets
Author
Prof.Dr.RamCharitraMaurya
Ph.D.,D.Sc,CChemFIC(India),CChemFRSC(UK)
ProfessorofInorganicChemistry
FormerHead,DepartmentofChemistryandPharmacy,and
Dean,FacultyofScience
RaniDurgavatiUniversity
Jabalpur482001(M.P.),India
[email protected]
ISBN978-3-11-072725-8
e-ISBN(PDF)978-3-11-072728-9
e-ISBN(EPUB)978-3-11-072740-1
LibraryofCongressControlNumber:2020952731
BibliographicinformationpublishedbytheDeutscheNationalbibliothek
TheDeutscheNationalbibliothekliststhispublicationintheDeutscheNationalbibliografie;
detailedbibliographicdataareavailableontheInternetathttp://dnb.dnb.de.
©2021WalterdeGruyterGmbH,Berlin/Boston
Coverimage:Piranka/Gettyimages
Typesetting:IntegraSoftwareServicesPvt.Ltd.
Printingandbinding:CPIbooksGmbH,Leck
www.degruyter.com
Dedicatedto
Mywife
Mrs.UshaRaniMaurya,
whohasalwaysbeenasourceofinspirationforme
throughoutmygrowth
&
Mysons,AshutoshandAnimesh;daughter,Abhilasha;andson-in-law,Adarsh
for
encouragement

Preface
Duringmylongjourneyofteachingspanofmorethan40yearsinthreedifferent
universities at B.Tech., M.Sc., M.Phil. and Ph.D. levels, I had always realized the
lack of textbooks in Inorganic Chemistry that covers most of the topics for in-
depth teaching of the subject matters. Moreover, I was also in quest of reading
materialsintheformofresearchpapers,reviewsandbooks,sothatcurriculumat
Postgraduate, M.Phil. and Ph.D. coursework levels in any university of India and
abroad toocanberevisedforupdatingmanpowersinChemistryformanifoldap-
plications. The present book, entitled Inorganic Chemistry: Some New Facets, in-
corporating 10chapters, is designed tomeet out the objectives mentioned above.
Althoughmanymoretopicsarestillnotcoveredinthisbookonlybecauseoflook-
ing over the too much bulk of the book, they will be given attention in its next
volume.
The book also aims to assist students in preparing for competitive examina-
tions,viz.NET,GATE,SLETandDoctoralEntranceTest(DET)particularlyinIndia.
Each chapter ends with different multiple choice, short answer and long answer
questions, covering the topics discussed in the chapter to allow an opportunity to
thestudentsfortheirself-evaluation.
Incompletingabookofthisnature,oneaccumulatesgratefulnesstotheprevi-
ousauthorsandeditorsofbooks,researchpapers,reviewsandmonographsonthe
relevanttopics.Ihaveconsultedthesesourcesfreelyandborrowedtheirideasand
viewswithnohesitationinpreparingthepresentmanuscript.Thesesourcesareac-
knowledgedandlistedinbibliography,andIamhighlythankfultotheseauthors.
Moreover,thepresentbookistheoutcomeofmyteachingofthesubjectformore
than 40 years to several batches of Masters, M.Phil. and Ph.D. coursework students
attheDepartmentofChemistry,AtarraP.G.College,Atarra(BundelkhandUniversity,
Jhansi, U.P., India) and Rani Durgavati University, Jabalpur (M.P.), India. I have
benefitedenormouslyfromtheresponse,questionsandcriticismsofmystudents.
Looking over the problems of students inlearning thesubject, I have tried my
besttopresentthesubjectwithastudent-friendlyapproach,thatis,expressingitin
an interactive manner and in simple language with many illustrative examples.
Moreover, the mathematical parts wherever required are given in details to make
the subject easily understandable. Therefore, I hope that the book will serve as a
textforM.Sc.,M.Phil.andPh.D.courseworkstudentsofChemistry.
My endeavour will be amply rewarded if the book is found helpful to the stu-
dentsandteachers.Despiteseriousattemptstokeepthetextfreeoferrors,itwould
be presumptuous to hope that no error has crept in.Ishall be grateful to allthose
who may care to send their criticism and suggestions for the improvement of the
bookonmye-mailID([email protected]).
https://doi.org/10.1515/9783110727289-202
VIII Preface
The writing of this book was initiated in September 2018 at 4515 Wavertree
Drive, Missouri City, Texas 77459, USA, during our stay with my daughter, Dr.
Abhilasha,andson-in-law,Dr.Adarsh,forwhichtheydeservethanks.
Lastbutnottheleast,Iamthankfultomywife,Mrs.UshaRaniMaurya,forher
patient understanding of the ordeal which she had to undergo due to my almost
one-sided attention during the completion of this challenging task. I am also in-
debtedtomystudentsfortheirencouragementandcooperation.
October2,2020 RamCharitraMaurya
B-95,PriyadarshiniColony,DumnaAirportRoad, (Author)
Jabalpur(M.P.),India
Contents
Preface VII
ChapterI
Valenceshellelectronpairrepulsion(VSEPR)theory:principles
andapplications 1
1.1 Introduction 1
1.2 PostulatesofVSEPRtheory:SidgwickandPowell 1
1.3 RulesproposedbyGillespieandNyholm 1
1.3.1 Rule1.Spatialarrangementofelectronpairsaroundthecentral
atomofagivenmolecule/ion 1
1.3.2 Rule2.Regularandirregulargeometry:presenceofhybrid
orbitalscontainingbondpairsandlonepairs 3
1.3.3 Rule3.Effectofelectronegativity:repulsionsexertedbybond
pairsdecreaseastheelectronegativityofthebondedatom
increases 6
1.3.4 Rule4.Multiplebondsexertastrongerrepulsion 6
1.3.5 Rule5.Repulsionsbetweenelectronpairsinfilledshellsare
largerthanthosebetweenelectronpairsinincomplete
shells 6
1.4 ExceptionstotheVSEPRmodel,ligand–ligandrepulsionandthe
ligandclosepackingmodel 8
1.5 ApplicationsofVSEPRtheory 10
1.6 ShortcomingsofVSEPRtheory 20
1.7 Bentrule 21
1.7.1 ConsistencyofBent’srulewithGillespie’sVSEPRmodel 23
Exercises 23
ChapterII
Delocalizedπ-bondinginpolyatomicmolecules:molecularorbital
approach 27
2.1 Localizedanddelocalizedbonds 27
2.1.1 Localizedσ-andπ-bonds 27
2.1.2 Delocalizedπ-bond(s) 27
2.2 Basicprinciplesofmolecularorbitaltheory:polyatomic
moleculesorionsinvolvingdelocalizedπ-bonding 27
2.2.1 Variousstepsinvolvedinworkingoutdelocalizedπ-MOs 28
2.3 Delocalizedπ-bondinginnon-cyclicpolyatomicmolecules
orions 29
2.3.1 Ozonemolecule(O ) 29
3
2.3.2 Nitrogendioxide(NO )molecule 32
2
X Contents
2.3.3 Nitriteion(NO −) 35
2
2.3.4 Delocalizedπ-bondinginhydrazoicacid 38
2.3.5 Delocalizedπ-bondinginhydrazoicion(N −) 41
3
2.3.6 Delocalizedπ-bondinginnitrateion(NO −) 44
3
2.3.7 Delocalizedπ-bondinginBF 48
3
2.3.8 Delocalizedπ-bondinginCu Omolecule 50
2
2.4 Delocalizedπ-bondingincyclicmolecules 53
2.4.1 Benzene(C H ) 54
6 6
2.4.2 Cyclopentadienylradical(C H ·) 56
5 5
2.5 Delocalizedπ-bondingincyclicions 59
2.5.1 3,4–Diketocyclobutenedianion(C O 2−) 60
4 4
2.5.2 Delocalizedπ-bondinginC O 2− 62
5 5
2.5.3 Delocalizedπ-bondinginC O 2− 64
6 6
Exercises 66
ChapterIII
Chemistryofboraneandrelatedcompounds:structure,bonding
andtopology 71
3.1 Introduction 71
3.2 Importanceofboranes 71
3.3 Classificationofboranes 71
3.3.1 Closo-boranes 71
3.3.2 Nido-boranes 72
3.3.3 Arachno-boranes 73
3.3.4 Hypho-boranes 73
3.3.5 Conjuncto-boranes 73
3.4 Nomenclatureofboranes 75
3.5 Propertiesofboranes 76
3.6 Metallaboranes/metalloboranesorboranecomplexes 76
3.7 Bondingandtopologyofboranes 79
3.7.1 Bondinginboranesandhigherboranes/boronclusters:
molecularorbitalapproach 79
3.7.2 Molecularorbitalapproach 79
3.7.3 FormationofB–H–Bbond 80
3.7.4 FormationofB–B–Bbond 83
3.8 Topologyofboranes(Lipscomb’srule):styxfour-digitcodingof
bondinginboranes 87
3.8.1 UtilityofLipscomb’srule 88
3.8.2 ValidityofLipscomb’srule 88
3.8.3 CalculationoftotalnumberofVEsandnumberofbondsin
boraneswithoutmakinguseofLipscomb’srule 93