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9'3 __Ithesis Supervisor The Organometallic Chemistry of Ambident Acetone Dianions. Reactions with Group 4 and 14 Element Dihalides. By Tao Wang B.S., Chemistry Hefei Polytechnic University, 1982 M.S., Chemistry Southern Methodist University, 1990 Submitted to the Department of Chemistry in Partial Fulfillment of the Requirements for the Degree of Doctor of Philosophy at the Massachusetts Institute of Technology February !9'3 © Massachusetts Institute of Technology 1995 All rights reserved. Signature of Author -"- Department of Chemistry November 14, 1994 Certified by / / n X Dietmar Seyferth __IThesis Supervisor Accepted by I / v // Dietmar Seyferth, Chairman Departmental Committee on Graduate Students rrsE@e~.sli 2 This doctoral thesis has been examined by a Committee of the Department of Chemistry as follows: Professor Hans-Conrad zur Loye _I _ Chairman .N r9 I Professor Dietmar Seyferth - ~~~/ Thesis Supervisor A9 Professor Richard R. Schrock 3 The Organometallic Chemistry of Ambident Acetone Dianions. Reactions with Group 4 and 14 Element Dihalides. By Tao Wang Submitted to the Department of Chemistry on November 14, 1994 in partial fulfillment of the requirement for the degree of Doctor of Philosophy ABSTRACT Chapter One. Reactions of Group 4 Metallocene Dichlorides with Acetone Dianions 2 - Acetone dianions, [CH2C(O)CR 2] (R = Ph, H) react with group 4 metallocene dichlorides (M = Zr, Hf) as C, O dinucleophiles. The products in solution are (by VPO) monomeric 2-metallaoxa-3-methylenecyclobutanes, but in the solid state they are "dimers", 1,5-dimetalla-2,6-dioxa-3,7-dimethylenecyclooctanes. The structure of 1,1,5,5- tetrakis(rl 5 -cyclopentadienyl)-3,7-bis(diphenylmethylene)- 1,5-dizircona-2,6- dioxacycloocetane was determined by X-ray crystallography. Chapter Two. Reactions of Organosilicon Halides with the Ambident 1,1- Diphenylacetone Dianion 1,1-Diphenylacetone dianion reacts with diorganodichlorosilanes to give 1,1,5,5- tetraorgano-3,7-bis(diphenylmethylene)-1,5-disila-2,8-dioxacyclooctanes, while 1,1- diphenylacetone dianion reacts with diorganodifluorosilanes to give a positional isomer, 1,1,5,5-tetraorgano-3,7-bis(diphenylmethylene)-1,5-disila-2,6-dioxacyclooctane. The structures of 1,1,5,5-tetraphenyl-3,7-bis(diphenylmethylana)- 1,5-disila-2,8- dioxacyclooctane and 1,1,5,5-tetraphenyl-3,7-bis(diphenylmethylana)-1,5-disila-2,6- dioxacyclooctane were determined by X-ray crystallography. A ten-membered cyclic comound and a six-membered cyclic compound also were prepared by the reaction of 1,1- diphenylacetone dianion with 1,2-dichlorotetramethyldisilane and 1,3- dichlorohexamethyltrisilane, respectively. The structure of 1,1,2,2,6,6,7,7-octamethyl- 4 4,9-bis(diphenylmethylene)-1,2,6,7-tetrasila-3,10-dioxacyclodecane was determined by X- ray crystallography. Chapter Three. Reactions of Diphenylgermanium Dihalides with the Ambident 1,1- Diphenylacetone Dianion l,l-Diphenylacetone dianion reacts with diphenyldichlorogermane and diphenyldifluorogermane to give 1,1,5,5-tetraphenyl-3,7-bis(diphenylmethylene)-1,5- digerma-2,6-dioxacyclooctane. The structure of 1,1,5,5-tetraphenyl-3,7- bis(diphenylmethylene)-1,5-digerma-2,6-dioxacyclooctane was determined by X-ray crystallography. Chapter Four. Synthesis and Characterization of 1,1'-115- Bis(Dimethylvinylcyclopentadienyl) Group 4 Metal Dichlorides Lithium dimethylvinylsilylcyclopentadienide reacted with Group 4 metal chlorides to afford 1,1'-bis(dimethylvinylsilylcyclopentadienyl)group 4 metal dichlorides in good yield. In addition, o-1,l'-bis(dimethylvinylsilyl)benzene and 1,1'- bis(dimethylvinylsilyl)ferrocenealso were prepared. These monomers potentially could be used for cyclopolymerization. Thesis Supervisor: Dr. Dietmar Seyferth Title: Professor of Chemistry 5 TABLE OF CONTENTS ABSTRACT ................................................................. 3 Chapter One. Reactions of Group 4 Metallocene Dichlorides with Acetone Dianions INTRODUCTION................. .......... ..................... 111 RESULTS AND DISCUSSION ................... 14 EXPERIMENTAL SECTION ......................................................... 62 General comments ................................ 62 Vapor pressure osmometry ............................ 63 X-ray crystallography ................... 65 Preparation of 1,1-diphenylacetone dianion [Ph2CC(O)CH21 2- (TW-I-72, II-6) .................................. 77 Preparation of acetone dianion [CH2C(O)CH2]2- (TW-II-28) ........................ 77 I I Preparation of Cp2ZrCH2C(=CPh 2)0, 7 (TW-II-16, 20, 30, III-49).............. 77 I I Preparation of Cp2Hf CH 2C(=CPh 2)0, 8 (TW-IV-5, 38, 42) ..................... 80 Preparation of (CpMe) 2ZrCH2C(=CPh 2)0, 9 (TW-IV-27, 29, 34) .......... 83 ~I 1~~~ Preparation of Cp2ZrCH 2C(=CH 2)0, 10 (TW-II-33, IV-4, V-4) ................. 85 Preparation of Cp2Hf CH 2C(=CH 2)0, 11 (TW-IV-40, V- 13) ..................... 88 I I Preparation of (PPh 3)2 PtCHC(=O)CH 2, 17 (TW-IV-61, 65, 70) ................. 90 1 I Reaction of Cp2ZrCH2C(=CPh 2)0, 7 with HCI (TW-VI-10) ..................... 91 Attempted reaction of l,l-diphenylacetone dianin [Ph2CC()CH21 2 - with Cp2TiC12 (TW-III-43, IV-13 ....................................................... 92 2- Attempted reaction of 1,1-diphenylacetone dianin [Ph2CC(O)CH 2] with Cp*2ZrC12 (TW-II-43, 52) ................................. 94 6 I I Attempted reaction of Cp2ZrCH2C(=CPh 2)0, 7 with CO (TW-V-46) ............. 94 I I Attempted reaction of Cp 2ZrCH 2C(-CPh 2)0, 7 with (O=CH2 )n (TW-V-48)................................................. 94 I ! Attempted reaction of Cp2ZrCH2C(=CPh 2)0, 7 with O=CHPh (TW-IV-11, 31) ................................................. 96 Attempted reaction of Cp2ZrCH2C(=CPh 2)0, 7 with HC-=CPh (TW-III-22, 40)............................................................................ 96 I I Attempted reaction of Cp2ZrCH2C(=CPh 2)0, 7 with t-BuNC (TW -IV -6) ................................................................................... 97 I I Attempted reaction of Cp 2ZrCH 2C(=CPh 2)0, 7 with Et-NC (TW-V-45)............................... ........................ 97 I I Mass spectra of Cp2TiCH 2C(=CPh 2)0,1 5 ........................................... 97 REFERENCES ............................................................................ 102 Chapter Two. Reactions of Organosilicon Halides with the Ambident 1,1- Diphenylacetone Dianion INTRODUCTION.......... ....... ........................108..........108 RESULTS AND DISCUSSION ....................................................... 110 EXPERIMENTAL SECTION ...................................................... 164 General comments ........................................................................ 164 Vapor pressure osmometry ...................................................... 166 X-ray crystallography .................................................................... 168 7 Structure of 1,1 ,5,5-tetraphenyl-3,7-bis(diphenylmethylene) -1,5-disila-2,8-dioxacycloocetane, 8 .................................................. 168 Structure of 1,1,5,5-tetraphenyl-3,7-bis(diphenylmethylene) -1,5-disila-2,6-dioxacycloocetane, 10 ................................................. 175 Structure of 1,1,2,2,6,6,7,7-octamethyl-4,9-bis(diphenylmethylene) -1,2,6,7-tetrasila-3,10-dioxacyclodecane, 11......................................... 182 2 Preparation of 1,1-diphenylacetonedianion [Ph2CC(O)CH2] - (TW-I-72, II-6) ................................................... 188 Preparation of 1,1,5,5-tetramethyl-3,7-bis(diphenylmethylene) -1,5-disila-2,8-dioxacycloocetane, 5 (TW-II- 13, III-69, 71) ....................... 188 Preparation of 1,1,5,5-tetraethyl-3,7-bis(diphenylmethylene) -1,5-disila-2,8-dioxacycloocetane, 6 (TW-III-67, 75)............................... 191 Preparation of 1,5-dihydrido-1,5-dimethyl-3,7-bis(diphenylmethylene) -1,5-disila-2,8-dioxacycloocetane, 7 (TW-III-66, 68) ............................... 192 Preparation of 1,1,5,5-tetraphenyl-3,7-bis(diphenylmethylene) -1,5-disila-2,8-dioxacycloocetane, 8 (TW-IV-30, V-50)............................ 193 Preparation of 1,1,5,5-tetraethyl-3,7-bis(diphenylmethylene) -1,5-disila-2,8-dioxacycloocetane, 9 (TW-V-3, VI-12) ............................. 195 Preparation of 1,1,5,5-tetraphenyl-3,7-bis(diphenylmethylene) -1,5-disila-2,6-dioxacycloocetane, 10 (TW-IV- 17, 22) ............................. 196 Preparation of 1,1,2,2,6,6,7,7-octamethyl-4,9-bis(diphenylmethylene) -1,2,6,7-tetrasila-3,10-dioxacyclodecane, 11 (TW-I-48, 50, 52, IV-7)......... 197 Preparation of 1,1,2,2,3,3-hexamethyl-5-diphenylmethylene -1,2,3-trisila-4-oxacyclohexane, 12 (TW-III-56, 61, 70, IV-10) ................. 199 Preparation of Ph2 CHC(O)CH2SiMe2CH2C(=O)CHPh2,13 (TW-III-72) .................................................. 200 Preparation of Ph2CHC(=CH2)OSiMe2SiMe2OC(--CH2)CHPh2,14 (TW-III-58, 64, 73)................................................... 201 Preparation of Ph2C=C(CH3)OSiMe3, 17a (PL) .................................... 202 Preparation of Ph2 C=C(CH 3)OSiMe2t-Bu, 17b (PL) ............................... 203 Preparation of CH2=C(OSiMe3)CHPh2, 18 (PL) .................................... 204 Preparation of Ph2C=C(CH2SiMe3)OSiMe3, 19 (TW-IV-72) ..................... 205 Preparation of Ph2 C=C(CH2SiMe2H)OSiMe2H, 20 (PL).......................... 206 Preparation of Ph2 C=C(CH2SiMe3)OSiMe2t-Bu, 21 (PL)......................... 207 Preparation of Ph2C=C(CH2SiMe3)OSiPh2Me, 22 (PL) ........................... 208 Preparation of Ph2C=C(CH2SiMe3)OSiMe2H, 23 (PL)...........................
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