Synthesis of supramolecular architectures using P_1tnn-ligands as building blocks [Elektronische Ressource] / vorgelegt von Shining Deng

Sophie Grimault

Informations

• Publié par: universitat_regensburg
• Publié le: 01 janvier 2008
• Nombre de lectures: 23
• Langue: Deutsch
• Poids de l'ouvrage: 4 Mo

Extrait

Synthesis of supramolecular architectures
using P -ligands as building blocks n





Dissertation zur Erlangung des
Doktorgrades der Naturwissenschaften (Dr. rer. nat.)
der Naturwissenschaftlichen Fakultät IV – Chemie und Pharmazie
der Universität Regensburg











vorgelegt von

Shining Deng

aus Nanjing, China

Regensburg 2007





































Diese Arbeit wurde angeleitet von Prof. Dr. Manfred Scheer.
Promotionsgesuch eingereicht am: 28.März.2007
Tag der mündlichen Prüfung: 23.April.2007
Vorsitzender: Prof. Dr. Rainer Winter
Prüfungsausschuss: Prof. Dr. Manfred Scheer (1. Gutachter)
Prof. Dr. Henri Brunner (2. Gutachter)
Prof. Dr. Burkhard König
i











































Die vorliegende Arbeit wurde in der Zeit von Dezember 2002 bis März 2004 am Institut für
Anorganische Chemie der Universität Karlsruhe (TH) und von April 2004 bis März 2007
am Institut für Anorganische Chemie der Universität Regensburg unter Anleitung von
Herrn Prof. Dr. Manfred Scheer angefertigt.
ii



















Dedicated to my family





















iii
路漫漫其修远兮,吾将上下而求索
“The journey ahead is indistinct and long;
I see no ending, yet high and low I’ll search
with my will unbending”

Qu Yuan, chinese poet, 340-278 B.C.
































iv
Contents

1. Introduction 1

2. Research Objectives 9

3. Results and Discussion 10

3.1. Synthesis and Studies on the Properties of Phosphaferrocenes 10
5 t3.1.1. Synthesis and studies on the properties of [Cp'''Fe( η -P C Bu)] 4
5 t and [Cp'''Fe( η -P C Bu )] 10 3 2 2
53.1.2. Synthesis and Studies on the Properties of [Cp'''Fe( η -P C PhH)] 14 3 2
53.1.3. e properties of [Cp'''Fe( η -P )] 17 5
3.2 Studies on the chemical properties and coordination
behaviour of the polyphosphaferrocene 18
5 t3.2.1. Triphosphaferrocene [Cp'''Fe( η -P C Bu )] as a ligand 18 3 2 2
5 t3.2.1.1. Reaction of [Cp'''Fe( η -P C Bu )] with CuCl 19 3 2 2
5 t3.2.1.1.1. [Cp'''Fe( η -P C Bu )] with CuCl in a stoichiometric ratio of 1:1 19 3 2 2
5 t3.2.1.1.2. [Cp'''Fe( η -P Bu C )] with CuCl in a stoichiometry ratio of 1:2 21 3 2 2
5 t3.2.1.2. Reaction of [Cp'''Fe( η -P C Bu )] with CuBr and CuI 25 3 2 2
5 t3.2.1.2.1. [Cp'''Fe( η -P C Bu )] with CuBr in a stoichiometric ratio of 1:1 25 3 2 2
5 t3.2.1.2.2. [Cp'''Fe( η -P Bu C )] with CuBr and CuI in a stoichiometric ratio of 1:2 29 3 2 2
5 t3.2.2. The Triphosphaferrocene [CpFe( η -P C Bu )] as a Ligand 34 3 2 2
5 t3.2.2.1. Reaction of [CpFe( η -P C Bu )] with CuCl 34 3 2 2
5 t3.2.2.2. Reaktion of [CpFe( η -P Bu C )] with CuBr 36 3 2 2
5 t3.2.2.3. η -P Bu C )] with CuI 37 3 2 2
5 t3.2.2.4. η -P Bu C )] with Ag[Al{OC(CF ) } ] 41 3 2 2 3 3 4
53.2.3. The triphosphaferrocene [Cp'''Fe( η -P C PhH)] as a ligand 43 3 2
53.2.3.1. Reaktion of [Cp'''Fe( η -P C PhH)] with copper halide 43 3 2
53.2.3.2. Fe( η -P C PhH)] with [(PtCl PEt ) ] 46 3 2 2 3 2
53.2.3.3. Fe( η -P C PhH)] with [W(CO) THF] 49 3 2 5
5 t3.2.4. The tetraphosphaferrocene [Cp'''Fe( η -P C Bu)] as a ligand 54 4
5 t3.2.4.1. Reaction of [Cp'''Fe( η -P C Bu)] with CuCl 54 4
5 t3.2.4.1.1. [Cp'''Fe( η -P C Bu)] with CuCl in a stoichiometric ratio of 1:1 54 4
v
5 t3.2.4.1.2. [Cp'''Fe( η -P C Bu)] with CuCl in a stoichiometric ratio of 1:2 57 4
5 t3.2.4.2. Reaktion of [Cp'''Fe( η - P C Bu)] with CuBr and with CuI 60 4
5 t3.2.4.2.1. Reaction of [Cp'''Fe( η -P C Bu)] with CuBr in a ratio of 1:1 60 4
5 t3.2.4.2.2. [Cp'''Fe( η - P C Bu)] with CuBr and CuI in a ratio of 1:2 63 4
5 t3.2.4.3. Reaktion of [Cp'''Fe( η - P C Bu)] with Ag[Al{OC(CF ) } ] 66 4 3 3 4
5 t3.2.4.4. Fe( η - P C Bu)] with AuCl[SC H ] 70 4 4 8
53.2.5. [Cp'''Fe( η -P )] as a Ligand in Coordination Chemistry 75 5
53.2.5.1. Reaction of [Cp'''Fe( η -P )] with CuCl 75 5
53.2.5.2. Fe( η -P )] with CuBr 80 5
53.2.5.2.1. Fe( η -P )] with CuBr in a ratio of 1:2 80 5
53.2.5.2.2. Reaction of [Cp'''Fe( η -P )] with CuBr in a ratio of 1:1 83 5
53.2.5.3. Fe( η -P )] with CuI 85 5
53.2.5.4. Fe( η -P )] with silver salt 88 5
53.2.5.4.1. Reaction of [Cp'''Fe( η -P )] with Ag[Al{OC(CF ) } ] 88 5 3 3 4
53.2.5.4.2. Fe( η -P )] with AgSO CF 92 5 3 3

4. Experimental 93

4.1 General remarks 93
4.1.1. Methods 93
4.1.2. Spectroscopy and analysis 93
4.2. Preparation of starting material 94
5 t 5 t4.2.1. Synthesis of [Cp'''Fe( η -P C Bu)] and [Cp'''Fe( η -P C Bu )] 94 4 3 2 2
54.2.2. [Cp'''Fe( η -P C PhH)] 95 3 2
54.2.3. Synthesis of [Cp'''Fe( η -P )] 96 5
5 t4.3. the complexes based on [Cp'''Fe( η -P C Bu )] 97 3 2 2
5 1 1 t4.3.1. Synthesis of [{Cp'''Fe( η : η : η -P C Bu )}( μ-CuCl)] (10) 97 3 2 2 2
4 1 14.3.2. [{(Cp'''Fe) ( η : η : η -P )}{ μ-CuCl} (MeCN)] (11) 97 2 4 2 ∞
4 1 1 t4.3.3. Synthesis of [{Cp'''Fe( η : η : η -P C Bu )}{ μ-CuBr(MeCN)}] (13) 98 2 2 2 2
4 44.3.4. [{(Cp'''Fe) ( η : η -P )}( μ-CuBr) (MeCN)] (14) 98 2 4 2 ∞
4 44.3.5. Synthesis of [{(Cp'''Fe) ( η : η -P )}( μ-CuI) (MeCN)] (15) 99 2 4 2 ∞
5 t4.4. the complexes based on [CpFe( η -P C Bu )] 99 3 2 2
5 1 1 t4.4.1. Synthesis of [{CpFe( η : η : η -P C Bu )}( μ-CuCl)(MeCN)] (16) 99 3 2 2 2
vi
5 1 1 t4.4.2. Synthesis of [{CpFe( η : η : η -P C Bu )}( μ-CuBr)(MeCN)] (17) 100 3 2 2 2
5 1 1 t4.4.3. η : η : η -P Bu C )} (CuI) MeCN] (18) 101 3 2 2 3 7
5 1 1 t4.4.4. Synthesis of [{CpFe( η : η : η -P Bu C )}( μ-AgMeCN)] (19) 101 3 2 2 2
54.5. the complexes based on [Cp'''Fe( η -P CPhH)] 102 3 2
5 1 14.5.1. Synthesis of [{Cp'''Fe( η : η : η -P C PhH)} (µ-CuBr) ] (20) 102 3 2 4 4 ∞
5 14.5.2. [Cp'''Fe( μ,η : η -P C PhH)PtCl PEt ] (21) 102 3 2 2 3
5 1 14.5.3. Synthesis of [{Cp'''Fe( μ, η : η : η -P C PhH)}{W(CO) } ] (22) 103 3 2 5 2
5 1 14.5.4. [{Cp'''Fe( μ, η : η : η -P C(CO) } ] (23) 103 3 2 5 3
5 t4.6 Synthesis of the complexes based on [Cp'''Fe( η -P CBu)] 104 4
4 t t4.6.1. Synthesis of [{Cp'''Fe( η -P C BuP(O) Bu)} {( μ-Cu Cl)(MeCN) }3 4 2 2 2
{( μ-CuCl) (MeCN)} ] (24) 104 2 2
5 1 1 1 t4.6.2. Synthesis of [{Cp'''Fe( η : η : η : η -P C Bu)} ( μ-CuCl) ] (25) 104 4 2 2 ∞
5 t t4.6.3. [{Cp'''Fe( η -P C Bu)} (P C Bu ) (Cu Br ) (MeCN) ] (26) 105 4 2 8 4 4 2 3 3 2 2
5 1 1 1 t4.6.4. Synthesis of [{Cp'''Fe( η : η : η : η -P C Bu)} ( μ-CuBr) ] (27) 105 4 2 2 ∞
5 1 1 1 t4.6.5. Syntheses of [{Cp'''Fe( η : η : η : η -P C Bu)} ( μ-CuI) ] (28) 106 4 2 2 ∞
5 1 1 t 5 1 t4.6.6. Syntheses of [Ag {Cp'''Fe( η : η : η -P C Bu)} {Cp'''Fe( η : η -P C Bu)} ] 2 4 2 4 2
[Al{OC(CF ) } ] (29) 106 3 3 4 2
5 1 t4.6.7. Syntheses of [CpFe( η : η -P BuC) AuCl(SC H )] (30) 107 4 4 8
54.7. S