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Publié par | julius-maximilians-universitat_wurzburg |
Publié le | 01 janvier 2006 |
Nombre de lectures | 24 |
Langue | Deutsch |
Poids de l'ouvrage | 2 Mo |
Extrait
PRIMARY PHOSPHINE HALFSANDWICH
COMPLEXES OF IRON AND RUTHENIUM –
SYNTHESIS AND HYDROPHOSPHINATION
REACTIONS
Dissertation zur Erlangung des naturwissenschaftlichen
Doktorgrades der Bayerischen Julius-Maximilians-Universität
Würzburg
vorgelegt von
Katharina Klüh
aus Fulda
Würzburg 2006
Eingereicht am: _________________________________________________________
bei der Fakultät für Chemie und Pharmazie
1. Gutachter: ____________________________________________________________
2. Gutachter:
der Dissertation
1.Prüfer: _______________________________________________________________
2.Prüfer: _______________________________________________________________
3.Prüfer: _______________________________________________________________
des öffentlichen Promotionskolloquiums
Tag des öffentlichen Promotionskolloquiums: ___________________________________
Doktorurkunde ausgehändigt am: _____________________________________________
Die vorliegende Arbeit wurde in der Zeit von
November 2002 bis Mai 2006
am Institut für Anorganische Chemie der Universität Würzburg
unter der Leitung von Prof. Dr. Wolfgang Malisch durchgeführt
Meinen Eltern
___________________________________________________________________________
CONTENTS
INTRODUCTION 1
I Synthesis of Functionalized Secondary and Tertiary
Phosphines via Hydrophosphination of Acrylonitrile,
Ethylisocyanate or Methyl-1,3-butadiene-1-carboxylate
with the Primary Phosphine Iron Complexes
{R’ C (OC) Fe[P(R)H ]}BF (R = i-Pr, t-Bu, Mes, Ph; 5 5 2 2 4
R’ = H, Me) 8
Abstract 9
Introduction 9
Results and Discussion 10
Synthesis of the Iron Complex {H C (OC) Fe[P(i-Pr)H ]}BF(3) 10 5 5 2 2 4
Hydrophosphination of Acrylonitrile (5) with {R’ C (OC) Fe[P(R)H ]}BF5 5 2 2 4
(R = i-Pr, t-Bu, Mes; R’ = H, Me) (3,4a,b) 11
Hydrophosphination of Ethylisocyanate (9) with the Secondary Phosphine
Iron Complex {H C (OC) Fe[P(i-Pr)(H)CH CH CN]}BF(6a) 14 5 5 2 2 2 4
Synthesis of the Tertiary Phosphine Iron Complexes {H C (OC) Fe[PPh 5 5 2
(CH CH=CHCH CO Me)(R)]}BF [R = CH CH CN, C(O)NHEt] (13a,b) via 2 2 2 4 2 2
successive Hydrophosphination of Methyl-1,3-butadiene-1-carboxylate (11) and
Acrylonitrile (5) or Ethylisocyanate (9) using [H C (OC) FeP(Ph)H ]BF (4c) 15 5 5 2 2 4
I ___________________________________________________________________Contents
Molecular structure of {H C (OC) Fe[P(i-Pr)H ]}BF (3) and {H C (OC) Fe 5 5 2 2 4 5 5 2
[PhP(CH (CH) CH CO Me)(CH CH CN)]}BF (trans-13a) 18 2 2 2 2 2 2 4
Experimental Section 21
References 31
Table of Compounds 33
II Primary Phosphine Ruthenium Complexes H C (Ph P) 5 5 3
(H RP)RuCl (R = Ph, Mes, i-Pr, t-Bu, Cy) and [H C (Ph P)2 5 5 3 2
Ru[P(Ph)H ]BF : Synthesis and Hydrophosphination of 2 4
Methylacrylate 34
Abstract 35
Introduction 35
Results and Discussion 36
Primary Phosphine Ruthenium Complexes H C (Ph P)[H (R)P]RuCl 5 5 3 2
[R = Ph, Mes, i-Pr, t-Bu, Cy] (3a-e) and [H C (Ph P) Ru[P(Ph)H ]BF(5) 36 5 5 3 2 2 4
Hydrophosphination of Methylacrylate (6) with H C (Ph P)[H (Mes)P]RuCl 5 5 3 2
(3b) and [H C (Ph P) Ru[P(Ph)H ]BF(5) 38 5 5 3 2 2 4
II ___________________________________________________________________Contents
Molecular structure of {H C (Ph P) Ru[P(Ph)H ]}BF (5) and {H C (Ph P) 5 5 3 2 2 4 5 5 3
[(Mes)(MeCO CH CH )HP]RuCl (8) 41 2 2 2
Experimental Section 44
References 52
Table of Compounds 54
III Chelatephosphine Substituted Primary Phosphine Iron
and Ruthenium Complexes [H C (P )Fe[P(R)H ]BF5 5 [2] 2 4
[P = dppe, mppe, (R)-(+)-PROPHOS, (R,R)-(–)-DIOP; [2]
R = Ph, i-Pr] and [H C (DIOP)Ru[P(Ph)H ]BF : 5 5 2 4
Synthesis and Hydrophosphination of Acrylonitrile and
the Isocyanates RNCO (R = (S)-1-Phenylethyl, Et) 55
Abstract 56
Introduction 56
Results and Discussion 58
Primary Phosphine Iron and Ruthenium Complexes [H C (P )FeP(R)H ]BF5 5 [2] 2 4
[P = dppe, mppe, (R)-(+)-PROPHOS, (R,R)-(–)-DIOP; R = Ph, i-Pr] (5a-d) [2]
and [H C (DIOP)RuP(Ph)H ]BF(9) 585 5 2 4
III ___________________________________________________________________Contents
Hydrophosphination Reactions of Acrylonitrile (10) with [H C (P )Fe[P(R)H ]BF5 5 [2] 2 4
[P = mppe, (R)-(+)-PROPHOS, (R,R)-(–)-DIOP; R = Ph, i-Pr] (5b-d) and [2]
[H C (DIOP)Ru [P(Ph)H ]BF(9) 61 5 5 2 4
Hydrophosphination of the Isocyanates RNCO [R = (S)-1-phenylethyl, ethyl]
(13a,b) with [H C (P )Fe[P(Ph)H ]BF [P = dppe, mppe] (5a,b) 62 5 5 [2] 2 4 [2]
Molecular structure of [H C (DIOP)RuNCMe]BF (8) and {H C [Ph P 5 5 4 5 5 2
(CH ) Me P]Fe[PH(Ph)[(C=O)NHEt]]}BF (14b) 64 2 2 2 4
Experimental Section 67
References 83
Table of Compounds 85
IV Synthesis and Reactivity of Primary Phosphine Iron
Complexes {H C (L)[H CO(CH ) Ph P]Fe[P(R)H ]}BF5 5 3 2 2 2 2 4
(L = CO, PMe ; R = i-Pr, Ph, Mes) containing a Hemilabile 3
Ligand 86
Abstract 87
Introduction 87
Results and Discussion 89
IV ___________________________________________________________________Contents
Primary Phosphine Iron Complexes {H C (L)[H CO(CH ) Ph P]Fe[P(R)H ]}BF5 5 3 2 2 2 2 4
[L = CO, PMe ; R = i-Pr, Ph, Mes] (7a-c, 9a,b) 89 3
Hydrophosphination of Acrylonitrile (11) and Ethylisocyanate (13) with
{H C (L) [H CO(CH ) Ph P]Fe[P(R)H ]}BF [L = CO, PMe ; 5 5 3 2 2 2 2 4 3
R = i-Pr, Ph, Mes] (7a-c, 10a,b) 93
Molecular structure of {H C (OC) Fe[PPh (CH ) OCH ]}BF (3b) and 5 5 2 2 2 2 3 4
{H C (Me P)[H CO(CH ) Ph P]Fe(PMesH )}BF(10b) 97 5 5 3 3 2 2 2 2 4
Experimental Section 101
References 115
Table of Compounds 119
V Synthesis and Reactivity of Primary Phosphine
Ruthenium Complexes {H C (Ph P)[H CO(CH ) Ph P]Ru 5 5 3 3 2 2 2
[PRR’H]}BF (R = Ph, Mes; R’ = H, Ph) containing a 4
Hemilabile Ligand 120
Abstract 121
Introduction 121
Results and Discussion 122
V ___________________________________________________________________Contents
Synthesis of the Ruthenium Complexes {H C (Ph P)[H CO(CH ) Ph P]Ru 5 5 3 3 2 2 2
[PRR’H]}BF [R = i-Pr, Ph, Mes; R’ = H, Ph] (7;8a,b) 122 4
Hydrophosphination of Acrylonitrile (9) with {H C (Ph P)[H CO(CH ) Ph P]Ru 5 5 3 3 2 2 2
[PRR’H]}BF [R = i124 4
Experimental Section 127
References 133
Table of Compounds 134
VI X-Ray Structure Analyses 135
Introduction 136
{[HOiPr Si(C H )](OC) W} (W-W) 139 2 5 4 3 2
Cp(OC) W=P(sMes)-W(CO) Cp and Cp(OC) W-P(sMes)-W(CO)Cp 143 2 3 2 2 W=P(OMe)sMes 151 2
Cp(OC)Fe-SiMePhH 156 2
SUMMARY 160
ZUSAMMENFASSUNG 169
APPENDIX 178
VI