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Primary phosphine halfsandwich complexes of iron and ruthenium [Elektronische Ressource] : synthesis and hydrophosphination reactions / vorgelegt von Katharina Klüh

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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.

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Publié par
Publié le 01 janvier 2006
Nombre de lectures 24
Langue Deutsch
Poids de l'ouvrage 2 Mo





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