Synthesis and reactivity of rhenium carbon-chain complexes and other adducts of super-sized phosphines [Elektronische Ressource] / vorgelegt von Roland Gröbl

De
Synthesis and Reactivity of Rhenium Carbon-Chain Complexes and Other Adducts of Super-Sized Phosphines Den Naturwissenschaftlichen Fakultäten der Friedrich-Alexander-Universität Erlangen Nürnberg zur Erlangung des Doktorgrades vorgelegt von Roland Gröbl aus Monheim/Schwaben II Als Dissertation genehmigt von den Naturwissenschaftlichen Fakultäten der Friedrich-Alexander-Universität Erlangen-Nürnberg. Tag der mündlichen Prüfung: 30.09.2005 Vorsitzender der Promotionskommission: Prof. Dr. D.-P. Häder Erstberichterstatter: Prof. Dr. John A. Gladysz Zweitberichterstatter: Prof. Dr. Rolf W. Saalfrank III Meinen Eltern, meinem Bruder und allen, die mich kennen und mögen IV Die vorliegende Arbeit wurde in der Zeit von Januar 1999 bis August 2004 am Institut für Organische Chemie der Friedrich-Alexander-Universität Erlangen-Nürnberg unter der Anleitung von Prof. Dr. John A. Gladysz angefertigt, ohne den diese Arbeit nicht hätte entstehen können und dem ich für die Stellung des interessanten Themas danken möchte. V Table of Contents Table of Contents................................................................................................................... V List of Abbreviations..........................................................................................................
Publié le : samedi 1 janvier 2005
Lecture(s) : 22
Source : WWW.OPUS.UB.UNI-ERLANGEN.DE/OPUS/VOLLTEXTE/2005/247/PDF/ROLANDGROEBLDISSERTATION.PDF
Nombre de pages : 185
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Synthesis and Reactivity of Rhenium Carbon-Chain Complexes
and Other Adducts of Super-Sized Phosphines


Den Naturwissenschaftlichen Fakultäten
der Friedrich-Alexander-Universität Erlangen Nürnberg
zur
Erlangung des Doktorgrades


vorgelegt von
Roland Gröbl
aus Monheim/Schwaben
II

Als Dissertation genehmigt von den Naturwissenschaftlichen Fakultäten der Friedrich-
Alexander-Universität Erlangen-Nürnberg.






















Tag der mündlichen Prüfung: 30.09.2005
Vorsitzender der Promotionskommission: Prof. Dr. D.-P. Häder
Erstberichterstatter: Prof. Dr. John A. Gladysz
Zweitberichterstatter: Prof. Dr. Rolf W. Saalfrank III













Meinen Eltern, meinem Bruder
und allen, die mich kennen und mögen IV

























Die vorliegende Arbeit wurde in der Zeit von Januar 1999 bis August 2004 am Institut
für Organische Chemie der Friedrich-Alexander-Universität Erlangen-Nürnberg unter der
Anleitung von Prof. Dr. John A. Gladysz angefertigt, ohne den diese Arbeit nicht hätte
entstehen können und dem ich für die Stellung des interessanten Themas danken möchte. V
Table of Contents

Table of Contents................................................................................................................... V
List of Abbreviations.......................................................................................................... VII
List of Compounds ...............................................................................................................IX
List of Tables........................................................................................................................XI
List of Schemes ................................................................................................................. XIII
List of Figures...XVII
Zusammenfassung .............................................................................................................XIX
Abstract........................................................................................................................... XXIII
0 General Introduction........................................................................................................ 1
References .......................................................................................................................... 8
1 Synthesis of “Super-Sized” Tertiary Phosphines ........................................................ 13
1.1 Introduction ................................................................................................................ 13
1.2 Results And Discussion.............................................................................................. 16
1.2.1 Two-tailed phosphines....................................................................................... 18
1.2.2 A three-tailed phosphine.................................................................................... 29
1.2.3 Crystallography................................................................................................. 32
1.3 Summary..................................................................................................................... 36
1.4 Experimental............................................................................................................... 37
1.5 References .................................................................................................................. 47
2 Synthesis and Redox Chemistry of Dirhenium Complexes with Super-Sized
Phosphines as Stabilizing Ligands ................................................................................ 51
2.1 Introduction. 51
2.2 Results and Discussion ............................................................................................... 55
2.2.1 Synthesis of the rhenium precursor ................................................................... 55
2.2.2 Connection of a phosphine to the rhenium center............................................. 57 VI
2.2.3 Attempted coordination of superphosphine 1 to the rhenium center via
phosphine borane complex (3,5-(CH -4-C H CH CH ) C H ) P⋅BH3 6 4 2 2 2 6 3 3 3
(21).....................................................................................................................60
52.2.4 Methyl complexes (η -C Me )Re(NO)(PR )(CH ), key precursors to 5 5 3 3
carbon chain complexes.....................................................................................62
2.2.5 The synthesis of complexes with sp carbon chains spanning two rhenium
centers................................................................................................................68
2.2.6 Redox chemistry of ReC Re complexes with even numbered carbon chains ....74 n
5 5 + – + –2.2.7 Preparation of [(η -C H COCH )(η -C H )Fe] BAr (81 BAr ) ..........79 5 4 3 5 5 F F
+ –2.2.8 Characterization of the ferrocenium salt 81 BAr ........................................82 F
2.2.9 Chemical oxidation of 70...................................................................................85
2.2.10 IR measurements..............................................................................................86
2.2.11 NMR monitoring88
2.3 Summary .....................................................................................................................90
2.4 Experimentals..............................................................................................................92
2.5 References.................................................................................................................100
3 Super-Sized Tertiary Phosphines: Properties and Applications ..............................105
3.1 Introduction...............................................................................................................105
3.2 Results and Discussion .............................................................................................108
3.2.1 Superphosphines in catalysis ...........................................................................108
3.2.2 Superphosphine complexes with transition metals different from rhenium.....119
3.2.3 NMR measurements to estimate basicity of superphosphines .........................127
3.2.4 Steric parameters of superphosphines.............................................................134
3.3 Summary ...................................................................................................................138
3.4 Experimental .............................................................................................................140
3.5 References.................................................................................................................147
Präsentationen....155
Danksagung.........................................................................................................................157
Lebenslauf......159 VII
List of Abbreviations

1{H} proton decoupled
3-NBA 3-nitrobenzylalcohol
Ar aryl
– – BAr B(3,5-C H (CF ) )F 6 3 3 2 4
br broad
Bu butyl
Calcd calculated
δ chemical shift
CV cyclic voltammetry
Cy cyclohexyl
d doublet
DABCO diacabicyclo[2,2,2]octane
DBP 1-phenyldibenzophosphole
dec. decomposition
DFT density function theory
DSC differential scanning calorimetry
equiv equivalent or equivalents
Et ethyl
FAB (= LSIMS) fast atom bombardment
(= liquid secondary ion mass spectroscopy)
GC gas chromatography
Hal halogen
i-, o-, m-, p- ipso-, ortho-, meta-, para- positions in substituted phenyl
rings
i. e. id est
i-Pr isopropyl
IR infrared spectroscopy VIII
L ligand
m multiplet
M metal (in structures); mol/L
Me methyl
Mp melting point
MS mass spectrometry
NEt triethylamine 3
NMR nuclear magnetic resonance
OAc acetate
Pd/C palladium on carbon
Ph phenyl = C H 6 5
Pipz piperazine
s singlet (NMR), strong (IR)
ν stretching frequency (IR)
t triplet
t-Bu tertiary butyl
TGA thermogravimetric analysis
THF tetrahydrofuran
THT tetrahydrothiophene
TLC thinlayer chromatography
TMEDA N,N,N´,N´-tetramethylethylenediamine
tol tolyl = C H CH 6 5 3
vs very strong
vs. versus
w weak

IX
List of Compounds

(3,5-(H C-4-C H CH CH ) C H ) P 1 3 6 4 2 2 2 6 3 3
(3,4-(H C-4-C H CH CH ) C H ) P 2 3 6 4 2 2 2 6 3 3
(3,4,5-(H C-4-C H CH CH ) C H ) P 3 3 6 4 2 2 2 6 2 3
3,4-(H C-4-C H CH CH ) C H NO 8 3 6 4 2 2 2 6 3 2
3,4-(H C-4-C H CH CH ) C H NH 9 3 6 4 2 2 2 6 3 2
+ – + –3,4-(H C-4-C H CH CH ) C H N BF 10 BF 3 6 4 2 2 2 6 3 2 4 4
3,4-(H C-4-C H CH CH ) C H I 11 3 6 4 2 2 2 6 3
(3,4-(H C-4-C H CH CH ) C H ) P⋅BH 12 3 6 4 2 2 2 6 3 3 3
3,5-(H C-4-C H C≡C) C H Br 14 3 6 4 2 6 3
3,5-(H C-4-C H CH CH ) C H 15 3 6 4 2 2 2 6 4
3,5-(H C-4-C H CH CH ) C H Br 16 3 6 4 2 2 2 6 3
(3,5-(H C-4-C H CH CH ) C H ) P⋅BH 21 3 6 4 2 2 2 6 3 3 3
3,4,5-(H C-4-C H C≡C) C H NO 22 3 6 4 3 6 2 2
3,4,5-(H C-4-C H C≡C) C H NH 23 3 6 4 3 6 2 2
+ – + –3,4,5-(H C-4-C H CH CH ) C H N BF 24 BF 3 6 4 2 2 3 6 2 2 4 4
3,4,5-(H C-4-C H CH CH ) C H I 25 3 6 4 2 2 3 6 2
(3,4,5-(H C-4-C H CH CH ) C H ) P⋅BH 26 3 6 4 2 2 2 6 2 3 3
5 + – + –[(η -C Me )Re(NO)(P(C H -3,4-(CH CH -4-C H CH ) ) )(CO)] BF 35 BF 5 5 6 3 2 2 6 4 3 2 3 4 4
5 + – + –[(η -C Me H -3,5-(CH CH -4-C H CH ) ) )(CO)] BF 36 BF 5 5 6 3 2 2 6 4 3 2 3 4 4
5(η -C Me )Re(NO)(P(C H -3,5-(CH CH -4-C H CH ) ) )(CHO) 37 5 5 6 3 2 2 6 4 3 2 3
5(η -C Me H -3,5-(CH CH -4-C H CH ) ) )(CH ) 38 5 5 6 3 2 2 6 4 3 2 3 3
5[(η -C Me )Re(NO)(P(C H -3,5-(CH CH -4- 5 5 6 3 2 2
+ – + –C H CH ) ) )(HC≡CC≡CSiMe )] BF 59 BF 6 4 3 2 3 3 4 4
5(η -C Me )Re(NO)(P(C H -3,5-(CH CH -4-C H CH ) ) )(C≡CC≡CSiMe ) 60 5 5 6 3 2 2 6 4 3 2 3 3
5(η -C Me H -3,5-(CH CH -4-C H CH ) ) )(C≡CC≡CH) 61 5 5 6 3 2 2 6 4 3 2 3
5(η -C Me )Re(NO)(P(C H -3,5-(CH CH -4-C H CH ) ) )(C≡C) ((3,5-(H C- 5 5 6 3 2 2 6 4 3 2 3 4 3
54-C H CH CH ) C H ) P)(ON)Re(η -C Me ) 70 6 4 2 2 2 6 3 3 5 5X
5(η -C Me )Re(NO)(P(C H -3,4-(CH CH -4-C H CH ) ) )(C≡C) ((3,4-(H C-5 5 6 3 2 2 6 4 3 2 3 4 3
54-C H CH CH ) C H ) P)(ON)Re(η -C Me ) 716 4 2 2 2 6 3 3 5 5
5 + + –[(η -C Me )Re(NO)(P(C H -3,5-(CH CH -4-C H CH ) ) )(HC≡CH)] 72 BF 5 5 6 3 2 2 6 4 3 2 3 4
5[(η -C Me H -3,5-(CH CH -4-C H CH ) ) )(C≡CH)] 73 5 5 6 3 2 2 6 4 3 2 3
5(η -C Me )Re(NO)(P(C H -3,5-(CH CH -4-C H CH ) ) )(C≡C) ((3,5-(H C- 5 5 6 3 2 2 6 4 3 2 3 3 3
54-C H CH CH ) C H ) P)(ON)Re(η -C Me ) 74 6 4 2 2 2 6 3 3 5 5
5(η -C Me )Re(NO)(P(C H -3,5-(CH CH -4-C H CH ) ) )(C≡C) ((3,5-(H C- 5 5 6 3 2 2 6 4 3 2 3 2 3
54-C H CH CH ) C H ) P)(ON)Re(η -C Me ) 75 6 4 2 2 2 6 3 3 5 5
5 5(η -C H COCH )(η -C H )Fe 81 5 4 3 5 5
5 5 + – + –[(η -C H COCH )(η -C H )Fe] BAr 81 BAr5 4 3 5 5 F F
trans-[((3,5-(H C-4-C H CH CH ) C H ) P) PdCl ] 90 3 6 4 2 2 2 6 3 3 2 2
trans-[(C F )((3,5-(H C-4-C H CH CH ) C H ) P) PtCl] 92 6 5 3 6 4 2 2 2 6 3 3 2
((3,5-(H C-4-C H CH CH ) C H ) P)W(CO) 95 3 6 4 2 2 2 6 3 3 5
((3,4,5-(H C-4-C H CH CH ) C H ) P)W(CO) 96 3 6 4 2 2 2 6 2 3 5
(3,5-(H C-4-C H -CH CH ) C H ) PSe 97 3 6 4 2 2 2 6 3 3
(3,4,5-(H C-4-C H CH CH ) C H ) PSe 98 3 6 4 2 2 2 6 3 2
(3,4-(H C-4-C H CH CH ) C H ) PSe 99 3 6 4 2 2 2 6 3 3
(3,5-(CH ) C H )PSe 100 3 2 6 3
(3,5-(CH ) C H )P 101 3 2 6 3
+ – + –[(3,5-(H C-4-C H CH CH ) C H ) PH] BF 102 BF3 6 4 2 2 2 6 3 3 4 4


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