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Ne1~~L~------¥", ~ ~1:C SYNTHESIS and CHA.H.ACTEHIZATION of GROUP IB and IIB METAL COMPLEXES with DITBRTIARY PHOSPHINE and DITERTIARY ARSINE LIGANDS

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Ne1~~L~------¥ YOUf JGSTCJ\i,7l STATE Uf H\'ERSITi GRADUATE SCHOOL THESIS Submitt ed in Partial Fu.l..fillment c,f the Rcquh·er:'..ents For th.e Degree elf Master of Science TITLE Synthesis and Characterization of Group IB and IIB Metal Complexes with Ditertiary Phosphine and Ditertiary Arsine Ligands PRESENTED BY Raj al M. Vyas ACCEPTED BY TI -iE DEPARTMENT OF Chemistry 'fief"1t dlli~~~l1r.~;~~i~---------,l~~_(ll~ 1 ne1~~l~------¥", ~ ~1:c SYNTHESIS AND CHA.H.ACTEHIZATION OF GROUP IB AND IIB METAL COMPLEXES WITH DITBRTIARY PHOSPHINE AND DITERTIARY ARSINE LIGANDS by Raj al M. "Vyas Submitted in Partial Fulfillment of the Requirements for the Degree of Master of Science in the Chemistry Program n1"'t 2 S l~ 72' Adviser Date Dean Youngstown State University June, 1 972 ii ABSTRACT SYNTHESIS AND CHARACTERIZATION OF G.nOUP IB AND IIB METAL COMPLEXES WITH DITERTIARY PHOSPHINE AND DITERTIAY ARSINE LIGANDS Rajal M. Vyas Master of Sci~nce in Chemistry Youngstown State University, 1972 This investigation describes the preparation and properties of complexes of the metals copper, silver, gold, zinc, cadmium, mercury, and nickel with di tertiary phos­ phine and ditertiary arsine ligands. The experimental work done is described in three parts: (a) Triphenylphosphine complexes. Some of these have been reported in the literature. Triphenylphosphine complexes of zinc, mercury, copper, and silver have been made either in the molten state1 by heating a mixture of metal halides and triphenylphosphine, or by mixing hot alcoholic solutions of the reactants. 2 Analytical infor­ mation is either completely lacking or at best is only partially reported. An attempt has been made in this study to prepare these complexes in ethanol solvent and determine their complete elemental analysis where feasible. (b) Ditertiary phosphine complexes. Ditertiary phosphine complexes of the halides of zinc, cadmium, mercury, copper, silver, gold, and nickel having a 'iOUNGSIU~~N SIAlt u1-.1~1.l\w1ll -~ UBRARY, 2!:Jibbi iii composition of 1:1 ligand to metal halide ratio have been prepared, characterized and their properties studied in some detail. (c) Ditertiary arsine complexes. Ditertiary arsine complexes of the halides of copper, gold, and mercury having ligand to metal halide ratio of 1:1 have been isolated, characterized and their properties are studied in some detail. Attempts to isolate ditertiary arsine complexes of zinc, cadmium, silver and nickel were unsuccessful. ACKNOWLEDGMENT I would like to take this opportunity in expressing my indebtedness and thanks to Dr. Inally Mahadeviah for his suggestions and unlimited help in completing this project. Also, my special thanks to Dr. Robert Smith and Dr. Elmer Foldvary for their helpful criticism in improving this manuscript. Finally, I would like to express my gratitude to my parents who were a constant source of inspiration to me. V TABLE OF CON TENTS PAGE ABSTllACT. • • . • . • • • • . • . • . • • • • • • • . • • ii ACKNOWLEDGEivilii~T S • •••• ·• • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • iv TABI.aE OF CONTEllTS. • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • v LIST OF FIG Ult.ES •• •..•.•••..•....•••.•.•..•..•.•..•.• LIST OF TABLES . ••.......... ~ ........•.....•..•....•• CHAPTER I. INTRODUCTION .. • • • • . • . • . • . • . • • • . • • • . • • • • .1 II. :METAL-LIGAND BONDING WITH SPECIAL REFERENCE TO DOUBLB BONDING. • • . • . • . • • • . • • • • • • • • . • 3 Theories of Metal-Ligand Bonding........... 3 (A) Crystal Field Theory................. 3 (B) Valence Bond Theory (VBT) •• o••••·•••• 5 (C) Ligand Field Theory (LFT)............ 10 (D) Molecular Orbital Theory (MOT)....... 17 Double Bonding According to ~olecular Orbital Theory •.•......•...•....•... ~.... 20 Experimental Evidence for Double Bonding in Complexes . .. o. • • • • • • • • • • • • • • • • • • • • • • • • • • • 24 Classification of the Nore Common Ligands on the Basis of Their Double Bonding capacity. 27 (A) Strong ,r-Bonding Ligands............. 27 (B) Moderately strong -rr-Bonding Ligands.. 28 (C) poor -rr-Bonding Ligands............... 29 III. SYNTHESIS.................................... 30 Preparation . ............ • . 30 vi (A) Preparation of Triphenyl Phosphine Complexes of IB and IIB Metal Halides 30 - (1) Preparation of Dichlorobis(tri- ~~6f~:.:~~~:~~~~~~:~~~::~:.~::~~~~~.. 30 (2) Preparation of Dibromobis(tri­ ~henyl phosphine) Zinc(II), tPph ) znBr • • • • • . • • • • • • •. • • • • • • • • • • • • 30 3 2 2 (3) Preparation.of Diiodobis(tri­ ~henyl phosphine Zinc(II), (Pph ) ZnI ••......••••••••••••••.••• 31 3 2 2 (4) Preparation of Dichlorobis(tri- phenyl phosphine) Cadmium(II), (Pph ) CdC1 •.•••.• 31 3 2 2 o................. (5) Preparation of Dibromobis(tri- phenyl phosphine) Cadmium(II), (Pph ) CdBr ••..••••••••••••••••••.•• ·· 31 3 2 2 (6) Preparation of Diiodobis(tri­ phenyl phosphine) Cadmium(II), (Pph ) CdI •.••••.•.••.•••.•••••••.•• 32 3 2 2 (7) Preparation of Dichloro(tri- phenyl phosphine) Mercury(II), (Pph ) HgC1 •••••.••••••••••.••••.••• 32 3 2 2 (8) Preparation of Dibromobis(tri- phenyl phosphine) Mercury(II), (Pph HgBr ••••••••.••••.••••••••••• 33 3)2 2 (9) Preparation of Diiodobis(tri­ phenyl phosphine) Nercury(II), tPPh3)2I1gI2 ••..•..••..•.. • •.......... 33 (B) Preparation of Di tertiary Phosphine, (C6H5J2PCH2CH2P(C6H5)2, Complexes of IB and IIB Metal Halides.................. 33 (1) Preparation of Dichloro(ditertiary phosphine) Zinc(II), (Ph P(CH ) Pph )- 2 2 2 ZnCl..................................2 33 (2) Preparation o! Dtbr9mo(dttertiary phosp~ine) Zinc(IIJ, lPh PlCH J : 2 Pph JZnBr ••••••.•••••.•• 2; .•••••2 ~••••• 34 2 vii (3) Preparation of Dichloro(ditertiary phos:phine) Cadmium(II), (Ph2P(CH 2 )2- Pph2) CdC1 . 2 34 (4) Preparation of Dibromo(ditertiary phosphine) Cadmium(II), (Ph2P(CH2 )2- Pph2 JCdBr •• • • • • • • • • • • • • • • • • • • • • • • • • • 35 2 (5) Preparation of Diiodo(ditertiar) p~~;)gi¥;~.:~~~:~:::~:.::~~:::~~-~~- 35 (6) Preparation· of Dichloro(ditertiary phosphine) l✓l ercury(II), (Ph2P(CH2 )2- Pph2 JHgC1 :. • . • • • • • • • • • • . • • • • • . • • 2 35 (7)·Ereparation of Diiodo(ditertiar) P~~~)~~r~~-~~~~~~::::~:.::~~:::~~-~~- 36 (8) Preparation of Chloro(ditertiary p~~;)g~gr~.:~::~~::~:.::~~:::~~~~:... 36 (9) Preparation of Bromo(ditertiary J~~;)g~~;~-~~::~~::~:.::~?:::~?:?~... 37 (10) Preparation of Chloro(ditertiary I;~~;)R~cr ~. ~:~ :~~:: ~: .::~~:: :~~ ~ ~:. .. 37 (11) Preparation of Dichloro(ditertiary phos:phine) .Gold(II), (Ph2P(CH2 ) 2- Pph2 JAuC1 2 •. • 38 (12) Preparation of Dichloro(ditertiary ~~~;)~tgr;.~:~~~:~::~:.::~~:::~~:~~.. 38 (C) Pre:paration of Di tertiary Arsine (C6H5J2As(C~2 )2As(C6~5)2, Complexes of IB and IIB ~etal Halides............... 39 (1) Preparation of Chloro(ditertiary arsine) Copper(I), (Ph2As(CH2)2- AsPh2)CuCl........................... 39 viii (2) Preparation of Bromo(ditertiary arsine) Copper(I), (Ph As(CH ) - AsPh2)CuBr............................2 2 2 39 (3) Preparation of Dichloro(ditertiary arsine) Gold(II), (Ph2As(CH2 )2As- Ph2 )AuC12 •• • . • . • • . • . • • . • . • . • • . • • • • 39 (4) Preparation of Dichloro(ditertiary arsine) Mercury(II), (Ph2As(CH 2 ) 2- AsPh2 )HgC12 •. ~ • . • • . • . • . • • . • • • . • . • • • • 40 (5) Preparation of Dibromo(ditertiary arsine) Me rcury(II), (Ph2As(CH2 ) 2- AsPh2 )HgBr2 •• • • • • • • • . • • • • . • • . • . • . • 40 IV. ELEr-IENTAL ANALYSIS. • . • • • • • • • • • . • • . • • 41 (A) Carbon and Hydrogen.................... 41 (B) Halogen Analysis.................... • • • 41 (C) Determination of Metals................ 42 (1) Determination of Zinc................ 42 Procedure.. 42 (2) Determination of Nickel.............. 43 .Procedure. 4 3 (3) Determination of Copper by Iodometric r,•iethod. • 44 Procedure.. 44 V. RESULTS AlJD DISCUSSION. • . • . • • . • • 45 REFERE NCES.. • • • . • • . • • . • • • . • • • • . • • . • • • 49 LIST OF FIGURES FIGURE PAGE 1. Sketches showing the distribution of electron density ins, p, and d orbitals.............. 6 2. Energy level diagrams showing the splitting of a set of d orbitals by octahedral and tetrahedral ligand fields ••.•..•••••••••••••• 12 3. Heats of hydration of divalent first transi- tion metals ... ...... ~. 15 4. Molecular orbital diagram for a d 6 octahedral complex, no pi bonding.. • • • • . • • • . • • • • 18 5. Energy level diagrams showing "Tr-interactions can affect the ligand field stabilization energy. 19 6. Double and multiple pi bonding •.••..••.•••••• 22,23 List of Tables TABLE PAGE 1. Common Hybridizat~on in Transition Metal Complexes • • • • • • • • • • • • • • • 7 2. Distribution of d-electrons in an Octahedral Field • • • • • • • • • • • • • • • • 14 3. Force Constant of Metal.Carbonyls, Ketone, Carbon dioxide and Formaldehyde Group. 26 4. C-0 Stretching Frequency of Carbonyls and Substituted Carbonyl Compounds • • • • 26 Elemental Analysis . 46,47,48 1 CHAPTER I INTRODUCTION This investigation describes the synthesis and characterization of ditertiary phosphine, (C H ) PCH CH - 6 5 2 2 2 P(C6H5)2, and ditertiary arsine, (C 6H5 )2AsCH 2CH 2As(C6H5) 2 , complexes of some of the post-transition metals. A 11 ••complex , or "coordination compound", is a unit in which a metal atom or ion is bound in a definite geometric arrangement to a definite number of groups called ligands. Syste:na tizati.on of coordination compounds in terms of struc­ ture, properties, and reactions originated with Alfred Werner's theory proposed in 1893. Most of the experi­ mental work which influenced Werner's theory was done using ammonia
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