W&M ScholarWorks Dissertations, Theses, and Masters Projects Theses, Dissertations, & Master Projects 1971 Potential Five-Coordinate Titanium-Diketonate Complexes Pamela Bowen Barrett College of William & Mary - Arts & Sciences Follow this and additional works at: https://scholarworks.wm.edu/etd Part of the Inorganic Chemistry Commons, and the Organic Chemistry Commons Recommended Citation Barrett, Pamela Bowen, "Potential Five-Coordinate Titanium-Diketonate Complexes" (1971). Dissertations, Theses, and Masters Projects. Paper 1539624729. https://dx.doi.org/doi:10.21220/s2-phf3-f166 This Thesis is brought to you for free and open access by the Theses, Dissertations, & Master Projects at W&M ScholarWorks. It has been accepted for inclusion in Dissertations, Theses, and Masters Projects by an authorized administrator of W&M ScholarWorks. For more information, please contact [email protected]. POTENTIAL FIVE-COORDINATE TITANIUM- M -DIKETONATE COMPLEXES A T h e sis Presented to The Faculty of the Department of Chemistry The College of William and Mary in Virginia In Partial Fulfillment Of the Requirements for the Degree of Master of Arts By Pamela Bo B arrett 1971 APPROVAL SHEET This thesis is submitted in partial fulfillm ent of the requirements for the degree of Master of Arts A u th o r / Approved, May 1971 D av id W • Th omp s on , /PhTiD • C irila D^ordjevic, Ph.D, Melvjrn D • S o h iav elii, Ph • D • i i 5 04110 ACKNOWLEDGMENTS The w riter wishes to express her appreciation to Professor David W. Thompson, under whose guidance this inves­ tigation was conducted, for his direction and criticism throughout the investigation. The author is indebted also to Professor C irila Djordjevic and Professor Melvin D. Schiavelli for their careful reading and criticism of the manuscript. Finally, the author wishes to express a special note of thanks to her husband, Richard Barrett, for his invaluable encouragement and assistance. iii TABLE OP CONTENTS Page ACKNOWLEDGMENTS ......... ..................................... I l l LIST OP TABLES . .......................' ..................................... v i l LIST OP PIGURES.............................................................. v i l l ABSTRACT ..o»».o. x REACTIONS OP TITANIUM TETRAHALIDES WITH POTENTIAL t BIDENTATE UNINEGATIVE LIGANDS - LITERATURE SURVEY A. PRELIMINARY CONSIDERATIONS 1 B. A -DIKETONE DERIVATIVES 4 X. Historical Perspective 4 2® Di-Substituted Products 6 3® Adducts of -^-Diketones with Titanium 16 4® Mono-Substituted .^-Diketonate 17 Compounds with Titanium 5® Tri-Substituted -^-Diketonate Complexes 18 with Titanium 6® Tetra-Substituted>^-Diketonate Com- 21 pounds of Titanium f 0 . COMPOUNDS WITH 8-QUINOLINOL 21 1* Adducts of 8-Quinolinol 21 2® Mono-Substituted Complexes of 8- 32 Q u in o lin o l 3® Di-Substituted Complexes of Titanium 33 with 8-Quinolinol 4® Tris-Substituted Complexes of 8- 34 Q u in o lin o l 5® Tetra-Substituted Complexes of 36 Titanium with 8-Quinolinol D« COMPOUNDS WITH SALICYLALDEHYDJ3 41 1® Di-Substituted Complexes 41 2® Tetra-Substituted Complexes of 41 Titanium with 8-Quinolinol and Sallcylaldehyde iv TABLE OF CONTENTS CONT'D. E . SERIES OF OXIMES WITH TITANIUM 45 TETRAHALIDES 1. Adducts of Oximes with Titanium 45 Tetrahalides 2. Mono-Substituted Complexes of 49 Titanium with Oximes P . COMPLEXES OP TITANIUM TETRACHLORIDE 53 WITH ACETANILIDES 1• Di-Substituted Complexes of 53 Acetanilides' with Titanium 2e Tri-Substituted Complexes of 53 Acetanilides with Titanium G. SUMMARY 5 6 EXPERIMENTAL eeoeteeoeeceeoeooeodo 57 REAGENTS eeeoveeaooaeeaeeaeeaa 57 SOLVENTS fiea«e*oe«<»««»e««»e<si09 57 PREPARATIONS 53 General Reaction Procedures 58 j Preparation of 3-Cyano-2,4-pentanedione 59 Preparation of 2,2,6,6-tetramethyl-3»5- 63 heptanedione Reaction of Titanium Tetrachloride and 64 3-Cyano-2,4-pentanedione in a 1:2 Molar Ratio Reaction of Titanium Tetrachloride and 65 3-Cyano-2,4-pentanedione in a 1:3 Molar Ratio Preparation of Trichloro(3-cyano-2,4- 65 pentanedionato)titanium(IV) Preparation of Trichioro(1-phenyl-1 93 - 65 butanedionato)titanium(IV). Preparation of Tribromo(1-phenyl-1,3- 66 butanedionato)titanium(IV) v TABLE OP CONTENTS CONT’D* P a g e Preparation of Tribromo-2,2,6,6- 67 tetram ethyl-3,5-heptanedionatotitanium (IV) Preparation of Trichloro(2,4-pentane- 67 dionato)titanium(IV) Reaction of Dicyclopentadienyltitanium 68 dichloride with Acetylacetone Preparation of Trichloro(1-phenyl-1,3- 68 butanedionato)~pyridinetitanium( IV) Preparation of Trichloroacetylacetonato- 69 pyridinetitanium(IV) PHYSICAL MEASUREMENTS •••-••••••••..o'* 69 Molecular Weights 69 Conductance Measurements 71 Halide Determinations 71 Melting Points 71 Infrared Spectra 71 Nuclear Magnetic Resonance Spectra 72 Analysis 72 DISCUSSION AND RESULTS.......................'•••'••-•••••73 Preparative Chemistry 73 Trihalo(^-diketonato)titanium (lV) Complexes 85 Trichloro(3-cyano-2 94-pentanedionato)- 103 titanium(lV) Conclusion 108 POOTNOTES oeeoo 1t8 vi LIST OP TABLES T a b le Page t -^-DIKETONATE COMPLEXES .................................................... 22 2 8-QUIN0LIN0LATE COMPLEXES ........ 37 3 SALICYLALDEHYDATO COMPLEXES ................................. 46 4 OXIME DERIVATIVES ...... 51 5 ACETANILIDE DERIVATIVES .... ...................... 54 6 ANALYTICAL DATA ...........o. 76 7 MOLECULAR WEIGHT DATA . .................................... 77 8 CONDUCTANCE DATA ............. 78 9 CHARACTERISTIC INFRARED ABSORPTIONS BY ^-DIKETONATE COMPLEXES CONTAINING TERMINAL METHYL GROUPS ........ 93 10 C-N STRETCHING FREQUENCY OF METAL COMPLEXES .....oe.....o«. 107 vii LIST OP FIGURES Figure Page 1 Structural Possibilities for Compounds in the TiX^-LH System ..................................... 3 2 Generalized reaction scheme for the interaction of titanium tetrahalides with potential uninegative bidentate ligands • • 6oo»«*«ea99«e 3 3 Isomeric possibilities for_dihalobis (1-phenyl-1.3-butanedionationato)- titanium (IV) •»osooa»**e««» 13 4 UMR Spectra of IiX 2 ( b z a c ) 2Complexes » « 15 5 Isomeric possibilities for dihalobis- (8-quinolinolato)tltanium(IV) a * * « 35 6 Diagram of apparatus for the preparation of titanium enolate complexes » e e « 60 7 Diagram of apparatus immediately prior tO filtration aaaeaaoaaoee 6 l 8 Diagram of apparatus after filtrationa a 62 9 Diagram of filtering funnel used to dry compound a « e a aaaaaaa»ae 62 10 Beckmann thermometer «»o»0a«a»a 70 11 Infrared spectrum of trichloro(2,4-pentane- dionato)titanium(lV) as a Mull In NUjOl aaaaaaoaeaaasas 79 12 Infrared spectrum of Pyridine as a Mull I n Nlljj Ol oaseoaaaeaaaao 80 13 Infrared spectrum of trichloro-( 2,4- pentanedionato)-pyridinetitanium- * (IV) as a Mull in Uujol » « a « • » 81 14 Infrared spectrum of trichloro(1-penyl- 1,3“butanedionato)pyridinetltanlum- (IV) as a Mull in Nujol • « « * • « 82 viii LIST OF FIGURES CONT'D.> Figur Page 15 The structure of (TiCl^/POCl )2 • • • • • 8? 16 Infrared spectrum of tribromo(2,2.6,6- tetram ethyl-3,5-heptanedionato)- titanium(lV) as a Mull in Nujol . * • 89 17 Infrared spectrum of tribromo(1-phenyl- 1, 3-butanedionato)titanium(IV) as a Mull in Nujol » o • • .............................« • 90 j 18 Infrared spectrum of trichioro(1-phenyl- 1, 3-butanedionato)titanium(IV) as a Mull in Nujol • • « • ••«••••• 91 19 Infrared spectrum of trichloro(1,3- diphenyl-1,3-propanedionato)titanium- (IV) as a Mull in Nu^ol ? 0 « -92 20A B, 0, D-Hmr spectra for mixtures of trichloro(1-phenyl-1,3-butanedionato)- titanium(IV) and dichlorobis(1-phenyl- 1, 3-butanedionato ) tit anium( IV) « e e> « 96 20 Nmr spectra (shifts relative to internal TMS) 97 21 Nmr spectrum of tribrom o(1-phenyl-1,3- butanedionato)titanium(IV) in methylene chloride 93 22 Nmr spectrum of tribrom o(2,2,6,6-tetram ethyl- 3 95-heptanedionato)titanium(IV) In methylene chloride 99 23 Nmr spectrum of trichloro(2,2,6,6- tetram ethyl-3,5-heptanedionato)- titanium(IV) in chloroform • e « » • « 100 24 Postulated structure for trichloro(3-cyano- 2s4-pentanedionato)titanium(lV) « • « 104 25 Infrared spectrum trichioro(3-cyano- 2,4-pentanedionato)-titanium(IV) as a Mull llu 3 ol 0»«90c»0feo«o<>e 10 6 ix ABSTRACT The intent of this work was to investigate reactions of titanium tetrachloride and titanium tetrabromide with several enolizable A-diketones. These diketones usually coordinate to metal atoms as the anion via both oxygens• Particular attention was directed toward the preparation and characterization of potentially five-coordinate com­ plexes of the type X 3TiL, X = Cl* Br and L = A-diketonate anion* since few five-coordinate complexes of titanium have been reported« A«x)iketones used in this study include 2,^-pentanedione * 3-cyano-2,*l'-pentanedione, l-phenyl-l*3- butanedione, 1,3-diphenyl-l*3-propanedione* and 2*2,6*6- tetramethyl-3*5-heptanedione. In addition to preparing and characterizing X^TiL complexes* attempts were made to prepare two pyridine^adducts of the potentially five coordinate complexes» x POTENTIAL FIVE-COORDINATE TITANIUM- >3-DIKETONATE COMPLEXES REACTIONS OF TITANIUM TETRAHALIDES WITH POTENTIAL BIDENTATE UNINEGATIVE LIGANDS- LITERATURE SURVEY A. PRELIMINARY CONSIDERATIONS In recent years there has been a great deal of interest in the reactions of titanium tetrahalides with potential 1 -7 bidentate uninegative ligands such as 2,^-pentanedione , o 8 1-phenyl-1*3-butanedione , 1* 3-diphenyl-l* 3-propanedione * 9 10-12 3-methyl-2»^-pentanedione * 8-quinolinol * salicylalde- 1 2 ,1 3 1** lb hyde , dimethyIglyoxime , dipehnylglyoxime , benzil lb 15-16 monoxime , benzoylacetanilides