Synthetic, structural and reactivity studies of indenyl ruthenium complexes

SYNTHETIC, STRUCTURAL AND REACTIVITY STUDIES OF INDENYL RUTHENIUM COMPLEXES NG SIN YEE (B.Sc.(Hons.), NUS) A THESIS SUBMITTED FOR THE DEGREE OF DOCTOR OF PHILOSIPHY DEPARTMENT OF CHEMISTRY NATIONAL UNIVERSITY OF SINGAPORE 2006 Acknowledgments Acknowledgments I would like to express my gratitude to all those who have helped me in one way or another to complete this thesis. I am deeply indebted to my supervisors, Dr. Goh Lai Yoong and A/P Leong Weng Kee, for their invaluable encouragement and guidance. I wish to thank also my cosupervisors, A/P Marc Garland (Dept. of Chemical and Biomolecular Engineering, NUS) and Dr. Zhu Yinghuai (Institute of Chemical and Engineering Sciences (ICES), A*STAR) for their support. Thanks are also due to A/P W. K. Leong, Dr. L. L. Koh and Ms G. K. Tan from NUS for X-ray structures determination, Dr. R. D. Webster from the Research School of Chemistry, Australian National University for the electrochemical and EPR measurements; and Dr. W. Y. Fan for computational calculations. I am grateful to my past and present group members for helpful discussion and moral and social support: Dr. Z. Weng, Dr. X. Lu, Dr. R. K. S. Shin, Elaine Tay, Victor Ng, Kuan Seah Ling, Marlin Halim, Sim Hui Shan and Lau Hiu Fong, some of whom have turned my best friends. I also had the pleasure to work jointly with Tan Jialin, Fang Guihua and Chua Zhijie on related parts of my project. Especially, I would like to give my special thanks to my husband, Foo Chin Yuen, for believing in me and giving me the inspiration and moral support when it was most required. Without his patient love and understanding, I would not have completed my present work. I am also grateful to my parents, for their unconditional love, encouragement and motivation. Most importantly, I thank ICES for awarding me a research scholarship to pursue my doctorate degree. Table of Contents Table of Contents Summary……………………………………………………………………………… x Chart 1: Compounds encountered in this thesis……………………………………… .xv List of Tables………………………………………………………………………… xviii List of Figures……………………………………………………………………… .….xx List of Abbreviations…………………………………………………………… ……xxiii Chapter 1. General introduction 1.1 Coordination properties of the indenyl (Ind) ligand………………………………1 1.2 The effect of haptotropic shift in indenyl complexes…………………………… 1.3 Indenyl ruthenium [(Ind)Ru] complexes…………………………….………… 10 1.4 1.3.1 Reactivity studies of [(Ind)Ru] complexes………………………………11 1.3.2 [(Ind)Ru] complexes as catalysts……………………………………… .18 Objectives……………………………………………………………………… 21 Chapter 2. Reactivity studies of [IndRu] complexes towards P-, N- and S-containing ligands 2.1 Introduction………………………………………………………………………22 2.1.1 General properties and metal chemistry of 1,1’-bis(diphenylphosphino)ferrocene (dppf)………………………… 23 2.1.1.1 Spectroscopic properties……………………………………….24 2.1.1.2 Coordination modes……………………………………………25 2.1.1.3 Electrochemistry……………………………………… …… .27 i Table of Contents 2.1.1.4 2.1.2 Catalysis………………………………………………………28 General properties and catalytic applications of [(R)-1-[(S)-2(diphenylphosphino)ferrocenyl]ethyldicyclohexylphosphine] [(R)-(S)-Josiphos]…………………………………………………… …30 2.1.3 General properties of thiolates, heterocyclic thiolates and 1,1dithiolates 2.1.3.1 Ruthenium thiolato complexes……………………………… .31 2.1.3.2 Ruthenium complexes containing heterocyclic thione donors………………………………………………………… 34 2.1.3.3 2.2 Ruthenium complexes containing 1,1-dithiolate ligands………36 Results and Discussion 2.2.1 Reactions of [(L)Ru(PPh3)2Cl] (L = Cp 1a, Ind 1) with phosphine ligands 2.2.1.1 Reactions of with IndH(CH2)2PPh2, dppf and tripod……… .43 2.2.1.2 Reactions of 1a and with (R)-(S)- Josiphos and epimerization kinetics……………………………………….…50 2.2.1.3. Conclusion…………………………………………… ………55 2.2.2 Reactions of [(Ind)Ru(dppf)Cl] with N-containing ligands 2.2.2.1 Reaction of with CH3CN…………………………………….56 2.2.2.2 Reaction of with azide and cycloaddition reaction of the azido derivative with MeO2CC≡CCO2Me…………………… 57 2.2.2.3 Crystallographic studies……………………………………… 59 2.2.2.4 Conclusion………………………………………………….….61 ii Table of Contents 2.2.3 2.2.4 Reactions of [(Ind)Ru(dppf)Cl] with thiolates 2.2.3.1 Reactions of with thiolates and solvent dependence…………62 2.2.3.2 Reactions of and with HS(CH2)2PPh2…………………… .65 2.2.3.3 Crystallographic studies……………………………………… 67 2.2.3.4 Cyclic voltammetric and EPR measurements………………….70 2.2.3.5 Conclusion………………………………………………… …76 Reactions of [(Ind)Ru] complexes with heterocyclic thiols 2.2.4.1 Reactions of [(Ind)Ru(dppf)L] (3: L = dppf; [7]+: L = CH3CN)…………………………… …77 2.2.5 2.2.4.2 Crystallographic studies…………………………………….….82 2.2.4.3 Electrochemical studies……………………………………… 87 2.2.4.4 Reactions of [(Ind)Ru(CO)2]2 22 and [(Ind)Ru(CO)2I] 27…….91 2.2.4.5 Conclusion…………………………………………………… 94 Reactions of [(Ind)Ru] complexes with 1,1-dithiolates 2.2.5.1 Reactions of [(Ind)Ru(diphos)Cl] (3: diphos = dppf; 29: diphos = dppm) with dithiocarbamates………………… .95 2.2.5.2 Reactions of and 29 with alkyl xanthantes……………… 99 2.2.5.3 Reactions of and 29 with dithiophosphinates…………… 100 2.2.5.4 Reactions of 27 with NaS2CNEt2 and KS2COiPr………… .101 2.2.5.5 Crystallographic studies………………………………………103 2.2.5.6 Theoretical study of the lability of Ind ligand………….…….114 2.2.5.7 Electrochemical studies…………………………… ……… 116 2.2.5.8 Conclusion…………………………………………… …… 118 iii Table of Contents 2.3 Experimental 2.3.1 Reactions of [(L)Ru(PPh3)2Cl] (L = Cp 1a, Ind 1) with phosphine ligands 2.3.1.1 Reaction of with IndH(CH2)2PPh2……………………… 122 2.3.1.2 Reaction of with dppf…………………………………… 123 2.3.1.3 Reaction of with tripod…………………………………… 123 2.3.1.4 Reaction of with (R)-(S)-Josiphos……………………….…124 2.3.1.5 Reaction of 1a with (R)-(S)-Josiphos and epimerization kinetics……………………………………… .125 2.3.2 Reactions of with N-containing ligands 2.3.2.1 Reaction of with CH3CN………………………………… .127 2.3.2.2 Reaction of with NaN3 and cycloaddition of the azido derivative…………………………128 2.3.3 Reactions of with thiolates and solvent dependence 2.3.3.1 Reactions of with NaSR (R = Me, Et, Ph)………………….129 2.3.3.2 Small-scale reactions of with NaSMe in MeOH and THF – effect of solvent………………………………….……131 2.3.4 2.3.3.3 Reaction of with NaOMe (in THF-MeOH)……………… .131 2.3.3.4 Reaction of with HS(CH2)2PPh2………………………… 132 2.3.3.5 Reaction of with HS(CH2)2PPh2……………………… … 133 Reactions of with heterocyclic thiols 2.3.4.1 With 2-mercaptopyrimidine (HSPym)……………………… 134 2.3.4.2 With 2-mercaptobenzothiazole (HSbztz)…………………… 135 iv Table of Contents 2.3.4.3 2.3.5 2.3.6 With 2-mercapto-5-methyl-1,3,4-thiadiazole (HSmtdz)…… .135 Reactions of [7]PF6 with heterocyclic thiols 2.3.5.1 With HSPym……………………………………… .……… 136 2.3.5.2 With HSbztz………………………………………………… 137 2.3.5.3 With HSmtdz………………… .…………………………….138 Reactions of 22 with heterocyclic thiols 2.3.6.1 With 2,2-bis(dithio(benzothiazole))………………………… 138 2.3.6.2 With N,N-dithiobisphthalimide………………………………139 2.3.6.3 With dipyridyl disulfide………………………………………140 2.3.6.4 With 6,6’-dithiodinicotinic acid………………………………140 2.3.7 Reactions of 27 with HSbztz………………………………………… 141 2.3.8 Reactions of and 29 with dithiocarbamates 2.3.8.1 Reactions of with NaS2CNR2 (R = Me, Et, C5H10)……… .141 2.3.8.2 Reaction of 29 with NaS2CNEt2…………………………… .144 2.3.9 Reactions of and 29 with alkyl xanthates 2.3.9.1 Reactions of with KS2COR (R = Et, iPr)……………… .…144 2.3.9.2 Reaction of 29 with KS2COiPr……………………….……….145 2.3.10 Reactions of and 29 with dithiophosphinates 2.3.10.1 Reactions of with NaS2PR2 (R = Et, Ph)……………… .…146 2.3.10.2 Reactions of 29 with NaS2PR2 (R = Et, Ph)………………….146 2.3.11 Reaction of 27 with KS2COiPr…………………………………….……149 2.3.12 Reaction of 27 with TMNO.2H2O………………………………… .…149 v Table of Contents 2.3.13 Reactions of 27 with KS2COiPr and NaS2CNEt2 in the presence of TMNO.2H2O 2.3.13.1 Reaction of 27 with KS2COiPr in the presence of TMNO.2H2O………………………… ….150 2.3.13.2 Reaction of 27 with NaS2CNEt2 in the presence of TMNO.2H2O………………………… .151 Chapter 3. Catalytic investigation on [(Ind)Ru] complexes 3.1 3.2 Introduction…………………………………………………………… ………152 3.1.1 Homo-coupling of terminal alkynes………………………………… 152 3.1.2 Addition of carboxylic acids to terminal alkynes………………… .….154 Results and Discussion 3.2.1 Catalytic activity of [(Ind)Ru] complexes in homo-coupling of phenylacetylene, HC≡CPh 3.2.1.1 Catalytic activity of [(Ind)Ru(L)(L’)X] (LL’ = dppm, dppf, X = S-containing ligands) in homo-coupling of phenylacetylene, HC≡CPh………… … 157 3.2.1.2 Catalytic activity of 22 and 27 in homo-coupling of phenylacetylene, HC≡CPh…………… 160 3.2.2 Catalytic activity of 22 in cross-coupling of terminal alkyne and carboxylic acids…………………………… …….166 3.3 Conclusion…………………………………………………………………… .171 vi Table of Contents 3.4 Experimental 3.4.1 Catalytic activity of [(Ind)Ru(L)(L’)(X)] (LL’ = dppm, dppf; X = S-containing ligands) in homo-coupling of phenylacetylene, HC≡CPh………………………….172 3.4.2 Catalytic activity of 22 and 27 in homo-coupling of phenylacetylene, HC≡CPh…… …………….… 173 3.4.3 Catalytic activity of 22 towards cross-coupling of terminal alkyne and carboxylic acids………………………………… .173 Chapter 4. Reactivity studies of [(Ind)Ru] complexes towards Co(CO)44.1 Introduction 4.1.1 Heterobimetallic complexes containing half-sandwich ruthenium moiety…………………………… .……………………… 175 4.2 Results and Discussion 4.2.1 Reactions of [(Ind)Ru(L)(L’)Cl] (29: LL’ = dppm; 49: L = L’ = CO) with NaCo(CO)4……………………………………………………… .177 4.2.2 Reaction of with NaCo(CO)4…………………………………… … 180 4.2.3 Reaction of with NaCo(CO)4……………………………………… 184 4.3 Conclusion ………………………………………………………………….….187 4.4 Experimental 4.4.1 Reaction of 29 with NaCo(CO)4…………………………………….….188 4.4.2 Reaction of 49 with NaCo(CO)4…………………………………….….188 4.4.3 Reaction of with NaCo(CO)4…………………………………….… .189 vii Table of Contents 4.4.4 Reaction of with NaCo(CO)4…………………………………… .….190 4.4.5 Synthesis of [59]PF6……………… ……………………………… …191 Chapter 5. Synthesis of tethered [IndRu(II)] complexes 5.1 Introduction…………………………………………………………………… 192 5.2 Results and Discussion 5.2.1 Synthesis of [(η3,η3-C10H16)RuCl2(κ1P-LH)] (LH = IndH(CH2)2PPh2) 62 and its reaction with acid……………… 196 5.2.2 One-pot synthesis of tethered [IndRu(II)] complexes………………….200 5.3 Conclusion…………………………………………………………………… .210 5.4 Experimental 5.4.1. Synthesis of [(η3,η3-C10H16)RuCl2(κ1P-LH)] 62……….…….211 5.4.2. Synthesis of [(η3,η3-C10H16)RuCl(CH3CN)(κ1P-LH)] (CF3SO3) [62a]CF3SO3……………………………….………212 5.4.3. Synthesis of [(η5,κ1P-L)Ru(COD)]PF6 [63]PF6……… …….213 5.4.4. Synthesis of [(η5,κ1P-L)Ru(PPh3)Cl] 64….………………….214 5.4.5. Synthesis of [(η5,κ1P-L)Ru(PPh3)H] 65 ….………………….215 5.4.6. Sythesis of [(η5,κ1P-L)Ru(2,2’-bipyridyl)]PF6 [66]PF6 and [(κ1P-LH)Ru(2,2’-bipyridyl)Cl]PF6 [67]PF6….…………216 5.4.7. 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Organometallics 2004, 23, 2956. 256 [...]... presence of NEt3 also resulted in the cleavage of the indenyl ligand, giving [Ru(CO)2(Sbztz)2] 28 The lability of the indenyl ligand was observed to be influenced by the nature of both the co-ligands at the Ru center and the incoming 1,1-dithiolate ligands, as well as the solvent Hence, the reactions of 3 and [(Ind)Ru(dppm)Cl] 29 with dithiocarbamate resulted in dissociation of the indenyl ligand, giving... 1.2 The effect of haptotropic shift in indenyl (Ind) complexes The heightened ability of indenyl transition metal complexes to undergo modification of the ligand-to-metal connectivity (e.g η5 ↔ η3 ↔ η1; η5 ↔ η6), also known as “haptotropic shifts”, is widely investigated at the time, and is therefore characteristic of indenyl metal complexes The flexibility of indenyl transition metal complexes in haptotropic... of the PPh3 ligand by 2-electron donors, as well as the ready displacement of the chloro ligand by both anionic and neutral ligands 26 Its well-defined CpRu(PPh3)2 moiety is an attractive auxiliary wherewith to attach organic groups for studies on the effects of steric and electronic environment on the chemical 26a and catalytic 27 reactivity of the complex Owing to the chemical uniqueness of the indenyl. .. η3Binding (C) in metal complexes of groups 9 and 10 metals of groups 4 and 9 3 2 and η1-Ind complexes (D) for are well documented However, C and D modes are not common for group 8 metal complexes, the only examples being [PPN][Fe(η3-Ind)(CO)3] (C1) 4 and [Fe(η1-Ind)(η5-Cp)(CO)2] (D1) 5 Coordination mode E was observed in triple and tetra-decker Ru complexes, e.g E1 6 while F and G was found in Ru3(CO)12... xvii List of Tables List of Tables Table 1.1 Slip-fold parameters……………………………………………………….4 Table 2.1 Common coordination modes of dppf and their examples…………… 26 Table 2.2 Common coordination modes of 1,1-dithiolates and their examples……39 Table 2.3 Selected bond parameters of complexes 2, 3, [4]+ and [CpRu(dppf)Cl]…………………………………….……………… 47 Table 2.4 Selected bond lengths (Å) and angles (°) of 9 and [(Ind/Cp)Ru(dppe)(N3C2(CO2Me)2)]…………………………... system of the ligand, have weakened the Ind-M bond strength This has been attributed to the electron-accepting nature of the six-membered ring in the indenyl ligand 23 Calhorda and Veiros have carried out detail theoretical calculations on the η5 η3 coordination shift of Cp and Ind ligands in Mo complexes, [(η5-Cp’)(η5Cp)Mo(CO)2]2+ (Cp’ = Cp, Ind) 24 This study supported Kubas’s proposal, that the indenyl. .. chemical uniqueness of the indenyl ligand as discussed in the previous section, there has been a surge in the study of Ind transition metal complexes, including that of Ru complexes 28 The marked effect of the capping ligand on reactivity of the complex came to light with the synthesis of [(Ind)Ru(PPh3)2Cl] 1 (Ind = η5-C9H7) (Scheme 1.4(a)) some 16 years after that of its Cp analogue, 1a 29 [(Ind)Ru(PPh3)2Cl]... degree of distortion in the solid state of indenyl complexes can be discussed in terms of the slip-fold distortion parameters described by Taylor and Marder 11 The parameters are: (a) the slip parameter (Δ), (b) the hinge angle (HA) and (c) the fold angle 3 Chapter 1: General Introduction (FA) The table below shows the values of slip-fold parameters for true η5-, distorted η5-, and true η3- complexes. .. dimerization of phenylacetylene…… 158 Table 3.2 Effect of amines, coordinating solvents and base on yield of II……….162 Table 3.3 [LRu(CO)2]2 (L = Ind, Cp, Cp*) and catalyzed dimerization of PhC≡CH in the presence of piperidine…………………………… ….163 Table 3.4 Cross coupling of carboxylic acids to PhC≡CH catalyzed by 22………168 Table 4.1 Common atomic numbering scheme and selected bond parameters for 56, 4.6 and 4.7... bond lengths (Å) and angles (°) for 62 and [62a]+……………200 xix List of Figures List of Figures Figure 2.1 ORTEP diagram of 2…………………………………………………….46 Figure 2.2 ORTEP diagram of 3…………………………………………………….46 Figure 2.3 ORTEP diagram of 4…………………………………………………….47 Figure 2.4 ORTEP diagram of R-6…………………………………………… … 53 Figure 2.5 ORTEP diagram of 8…………………………………………………….60 Figure 2.6 ORTEP diagram of 9…………………………………………………….61 . SYNTHETIC, STRUCTURAL AND REACTIVITY STUDIES OF INDENYL RUTHENIUM COMPLEXES NG SIN YEE (B.Sc.(Hons.), NUS) A THESIS SUBMITTED FOR THE DEGREE OF DOCTOR. ligand………………………………1 1.2 The effect of haptotropic shift in indenyl complexes ………………………… 5 1.3 Indenyl ruthenium [(Ind)Ru] complexes ………………………….………… 10 1.3.1 Reactivity studies of [(Ind)Ru] complexes ……………………………11. dissociation of the indenyl ligand was observed. Likewise the reaction of [(Ind)Ru(CO) 2 I] 27 with HSbztz in the presence of NEt 3 also resulted in the cleavage of the indenyl ligand, giving