YTTERBIUM(II) – GROUP 6, 7 TRANSITION METAL CARBONYL COMPLEXES: SYSTEMATIC SYNTHESES AND STRUCTURAL CHARACTERIZATION DISSERTATION Presented in Partial Fulfillment of the Requirements for the Degree of Doctor of Philosophy in the Graduate School of The Ohio State University By Pavel V. Poplaukhin, B.S. ************ The Ohio State University, 2006 Dissertation Committee: Approved by Professor Sheldon G. Shore, Adviser _______________________ Professor Claudia Turro Advisor Professor Yiying Wu Professor Richard A. Miller Graduate Program in Chemistry ABSTRACT New carbonyl complexes of divalent ytterbium and transition metals of groups 6, 7 of the periodic table have been prepared. The syntheses were carried out in systematic fashion with the aim of establishing general procedures suitable for preparation of a range of compounds of this type. The products obtained were characterized by means of IR spectroscopy and X-ray single crystal diffraction. Nineteen X-ray structures are reported herein, of which only one has been published before. The compounds studied can be divided into two major groups: the solvent-separated ion pairs, where the YbII cation is surrounded with solvent molecules acting as ligands, preventing interaction with the metal carbonylate anion; and complexes with the bridging carbonyl ligands (isocarbonyl ligands), where the cation and the anion are bound together through a –CO- link. New instances of condensation of the solvent-separated ion pairs into the isocarbonyl complexes have been discovered, and the mechanism for such transformation was 2- proposed. The novel [Hg(W(CO)5)2] anion was discovered and characterized by X-ray single crystal diffraction. Its reactivity was briefly investigated. ii Посвящаю моим родителям Dedicated to my parents iii ACKNOWLEDGMENTS I would like to thank all the wonderful friends that I made during my stay here at OSU. This thesis would not be possible without their help and support. I wish to express my gratitude to my parents also, whose love and support I could sense all this time, no matter the distance. I am obviously indebted to Dr. Sheldon Shore for his advice, financial support, and remarkable freedom that I and my fellow coworkers enjoyed in his research group. I also cannot fail to mention Dr. Shore’s jokes and his easy-going personality, qualities that helped everyone working under his guidance. My special thanks go to Dr. Xuenian Chen, who was a true friend and teacher all these years. His knowledge, experience and almost unbelievable patience made this thesis possible. I am grateful to Dr. Edward A. Meyers for his inestimable help with X-ray structure determinations and many interesting conversations we held along the way. I thank Dr. Shengming Liu for teaching me many laboratory techniques and helping with X-ray, as well as being a great person to talk to. And I also want to thank all Shore group members that I worked with. It was fun to get to know you guys! iv VITA December 5, 1976……………...…Born – Biysk, Russia 1999…………………………….…B.S. Chemistry, Novosibirsk State University 1999 – 2001……………………….Graduate Research Assistant, Institute of Solid State Chemistry, Siberian Branch of Russian Academy of Sciences, Novosibirsk, Russia 2001 – present……………….…....Graduate Teaching and Research Associate, The Ohio State University PUBLICATIONS 1. Liu, S.; Poplaukhin, P.V.; Ding, E.; Plecnik, C.; Chen, X.; Keane, M.A.; Shore, S.G. “Extended Lanthanide-Transition Metal Arrays with Cyanide Bridges: Syntheses, Structures and Catalytic Applications”, J. of Alloys and Comp. 2006, 418, 21. v 2. Modestov A.N., Poplaukhin P.V., Lyakhov N.Z. “Dehydration kinetics of lithium sulfate monohydrate single crystals”, Journal of Thermal Analysis and Calorimetry, 2001, 65(1), 121-130. 3. Kundo N.N., Ivanchenko V.A., Mishakov I.V., Poplaukhin P.V. “Effects of an electron beam on aqueous solutions of Cr(VI) salts”, Khimiya v Interesakh Ustoichivogo Razvitiya (Chemistry for Sustainable Development), 1999, 5, 491-495. 4. Kundo N.N., Ivanchenko V.A., Mishakov I.V., Poplaukhin P.V. “Study of the influence of sulfurous reducing agents on Cr(VI) elimination from aqueous solutions”, Khimiya v Interesakh Ustoichivogo Razvitiya (Chemistry for Sustainable Development), 1999, 5, 485-490. 5. Klyuchnikov O.R., Brylyakov K.P., Poplaukhin P.V. “Reaction of 2,4,6-t-tret- butilphenol with 2-methyl-5-isopropyl-1,4-dinitrozobenzene”, Izvestiya Vysshih Uchebnyh Zavedeniy (in Russian), Part ‘Chemistry and Chemical Technology’, 1996, 39(1), 98-99. vi FIELDS OF STUDY Major Field: Chemistry vii TABLE OF CONTENTS Abstract……………………………………………………………………………………ii Dedication………………………………………………………………………………...iii Acknowledgments…………………………………….………………………………….iv Vita………………………………………………………………………………………...v List of Tables……………………………………………………………………………xiv List of Figures………………………………………………………………………..….xix List of Schemes…………………………………………………………………...….xxxiii List of Charts…………………………………………………………………………xxxv List of Abbreviations…………………………………………………………………xxxvi List of Compound Numbers………………………………………………………...xxxviii CHAPTER 1. Introduction 1.1 General Review of Ln - TM Complexes…………………………………………..1 1.2 Ln-TM Cyanides…………………………………………………………………..4 1.3 Ln-TM Carbonyls 1.3.1 General Remarks…………………………………………………..…………...8 viii 1.3.2 Systems with direct Ln–M bond…………………………………………...10 1.3.2 Solvent-Separated Ion Pairs………………………………………………..14 1.3.3 Systems with Bridging Ligands (Ln-TM Isocarbonyls)……………………………………………….…17 1.3.4.1 Transmetalation reaction…………………………………………………22 1.3.4.2 Reduction of Transition Metal Carbonyls over Amalgam……………….24 1.3.4.3 Condensation of Solvent-Separated Ion Pairs into Extended Arrays…………………………………………………...….26 1.4 Applications……………………………………………………………………..28 1.5 Statement of the Problem……………………………………………………….29 CHAPTER 2. Yb(II) – Group 7 Transition Metal Carbonyl Complexes 2.1 Starting Materials…………………………………………………………….31 2.2 Transmetalation reactions between Yb and Hg[M(CO)5]2 (M=Mn, Re). Formation of the Solvent-Separated Ion Pairs…………………………………..………….34 2.3 Solution IR Spectra of [Yb(THF)6][Mn(CO)5] 1, [Yb(THF)6][Re(CO)5] 2, [Yb(DME)n][Mn(CO)5]2 (1a), [Yb(DMF)n][Mn(CO)5]2 (1b), [Yb(pyr)6][Mn(CO)5]2 (1c)………………….37 2.4 X-ray structures of 1 and 2………………………………………………..….41 ix 2.5 Condensation of 1 with Et2O into extended structures {Yb(THF)2(Et2O)2[(μ-CO)2Mn(CO)3]2}∞ (3) and {Yb(THF)4[(μ-CO)2Mn(CO)3]2}∞ (4)…………………………………..53 2.6 Molecular Structure of {Yb(THF)2(Et2O)2[(μ-CO)2Mn(CO)3]2}∞ (3)………62 2.7 Molecular Structure of {Yb(THF)4[(μ-CO)2Mn(CO)3]2}∞ (4)………………64 2.8 Minor Products of Condensation of 1 with Et2O. Molecular Structures of (THF)2Mn3(CO)10 (5) and [(THF)5Yb(μ-CO)Mn3(CO)13][Mn3(CO)14] (6)…………………………67 CHAPTER 3. Yb(II) – Group 6 Transition Metal Carbonyl Complexes. - Complexes of the [CpM(CO)3] anions 3.1 Starting Materials…………………………………………………………….76 3.2 Notes on Syntheses…………………………………………………………..78 3.3 The Structure of {(THF)4Yb[Cp(μ-CO)Cr(CO)2][Cp(μ-CO)2Cr(CO)]}∞ (7a)………………..86 3.4 Molecular Structures of the 1-D Polymeric Chain Compounds {(THF)4Yb[Cp(μ-CO)2Mo(CO)]2}∞ (8a), {(THF)3Yb[Cp(μ-CO)2W(CO)]2}∞ (9a), {(CH3CN)4Yb[Cp(μ-CO)2Cr(CO)]2}∞ (7b), {(CH3CN)4Yb[Cp(μ-CO)2Mo(CO)]2}∞ (8b)………………………………...89 x 3.4.1 One-Dimensional Chain Structures 8a and 9a…………………………90 3.4.2 One-Dimensional Chain Structures 7b and 8b………………………...96 3.5 Molecular Structures of the Discrete Molecular Compounds (CH3CN)6Yb[Cp(μ-CO)W(CO)2]2 (9b) and (DME)3Yb[Cp(μ-CO)M(CO)2]2 (M = Cr, 7c; M = Mo, 8c; M = W, 9c)……………………………………...101 3.6 Discussion of the Solution Infrared Spectra………………………………..105 3.7 Discussion of the Molecular Structures…………………………………….109 CHAPTER 4. Yb(II) – Tungsten Carbonyl Complexes Derived from W(CO)6 4.1 Starting Materials…………………………………………………………...114 4.2 Reactions of the Ytterbium Amalgam with the Tungsten Hexacarbonyl in Various Solvents. Overview of Preparation of [Yb(DMF)7][W2(CO)10] (10), {(CH3CN)6Yb(W2(CO)10)·CH3CN}∞ (11) and {(pyr)5Yb[Hg(W(CO)5)2]}∞ (12)…………………………………………...115 4.3 Preparation, Molecular Structure and the Solution IR Spectrum of the Solvent-Separated Ion Pairs Complex [Yb(DMF)7][W2(CO)10] (10)………………………………..…...117 xi 4.4 Preparation, Molecular Structure and the Solution IR Spectrum of the 1-D Polymer {(CH3CN)6Yb(W2(CO)10)·CH3CN}∞ (11)…………………………………127 4.5 Preparation, Molecular Structure and the Solution IR Spectrum of the 1-D Polymer {(pyr)5Yb[Hg(W(CO)5)2]}∞ (12)…………………………………………...131 4.6 Reduction of {(pyr)5Yb[Hg(W(CO)5)2]}∞ (12) with Sodium Amalgam………………………………………….……….…138 4.7 Attempted Reduction of the Chromium Hexacarbonyl with the Ytterbium Amalgam………………………………………………142 CHAPTER 5. Conclusion………………………………………………………………146 CHAPTER 6. Experimental Section 6.1 General Procedures…………………………………………………………148 6.2 X-ray Structure Determination……………………………………………..149 6.3 Preparation of [Yb(L)n][M(CO)5]2 1a, 1b, 1c, 2…………………………....151 6.3.1 Route (a)………………………………………………………………...151 6.3.2 Route (b)………………………………………………………………..152 6.4 Preparation of {(THF)2(Et2O)2Yb[(μ-(CO)2Mn(CO)3)2]}∞, 3……………..152 6.5 Preparation of {(THF)4Yb[(μ-CO)2Mn(CO)3)2]}∞, 4………………………153 6.6 Preparation of (THF)2Mn3(CO)10, 5………………………………………..153 xii 6.7 Preparation of [(THF)5Yb(μ-CO)Mn3(CO)13][Mn3(CO)14], 6……………..154 6.8 Preparation of compounds 7a, 7b, 7c, 8a, 8b, 8c, 9a, 9b, 9c…………...….154 6.8.1 Preparation via the ytterbium amalgam route (Scheme 3.1)……………154 6.8.2 Preparation via the mercury bis-di(chromiumcyclopentadienyltricarbonyl) route (Scheme 3.2)…….155 6.8.3 Elemental analyses for compounds 7a, 7b, 7c, 8a, 8b, 8c, 9a, 9b, and 9c……………………………………………………………….155 6.9 Preparation of compounds 10, 11 and 12………………………………155 6.9.1 Preparation of [Yb(DMF)7][W2(CO)10] (10)……………………….156 6.9.2 Preparation of {(CH3CN)6Yb(W2(CO)10)·CH3CN}∞ (11)………….157 6.9.3 Preparation of {(pyr)5Yb[Hg(W(CO)5)2]}∞ (12)…………………...157 6.9.4 Preparation of (pyr)3Cr(CO)3 (13)………………………………….158 APPENDIX A.