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

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160 pages
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.
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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. Synthesis of the complexes based on [Cp'''Fe( η -P)] 108 5
5 1 1 14.7.1. [{Cp'''Fe( η : η : η : η -P )}( μ-CuCl)(MeCN)] (31) 108 5 ∞
5 1 1 14.7.2 Synthesis of [{Cp'''Fe( η : η : η : η -P )}( μ-CuBr)] (32) 108 5 ∞
5 1 14.7.3. [{Cp'''Fe( η : η : η -P )} ( μ-CuBr) ] (33) 109 5 4 3 ∞
5 1 14.7.4. Synthesis of [{Cp'''Fe( η : η : η -P )} ( μ-CuI) ] (34) 109 5 4 4 ∞
5 2 14.7.5. [Ag{Cp'''Fe( η η : η -P )} ] [Al{OC(CF ) } ] (35) 110 5 2 n 3 3 4 n
54.7.6. Reaction of [Cp'''Fe( η -P )] with AgSO CF 110 5 3 3

5. Conclusions 111

5 t5.1 Triphosphaferrocene [Cp'''Fe( η -P C Bu )] as a ligand 111 3 2 2
5 t5.2 The Triphosphaferrocene [CpFe( η -P C Bu )] as a Ligand 113 3 2 2
55.3 The Triphosphaferrocene [Cp'''Fe( η -P C PhH)] as a Ligand 114 3 2
5 t5.4 Tetraphosphaferrocene [Cp'''Fe( η -P C Bu)] as a ligand 116 4
55.5 Pentaphosphaferrocene [Cp'''Fe( η -P )] as a ligand 118 5
vii
6. Notes and References 121

7. Appendix 124
7.1. Directory of abbreviations 124
7.2. Directory of compounds 125
7.3. Crystallographic Data for the Reported Structures 127

8. Acknowledgments 150




















viii
1. Introduction

5 2- [1]Since the first synthesis of [Ti( η -P ) ] by Ellis and coworkers , the search for characterizable 5 2
decaphosphaferrocene complexes has been a challenge in the field of phosphorus-containing
[2] ¯ complexes. In addition, the lower phosphorus-containing complexes with [(RC) P ] ligands n 5-n
5(n = 1–3) are of particular interest since η -phospholyl complexes show activity in various
[3,4,5]homogeneous catalysis applications. Among the series of ferrocene complexes with
¯ [6] [7][(RC) P ] ligands (n = 0–5) the syntheses of A and E have been benchmarks in the n 5-n
[8]development of polyphospholyl complex chemistry.


R'R' R'
P
P PP P
Fe Fe Fe
RR R
ABB'
R'R'R' PR' P P PP PP PPPP PPPP
FeFeFeFe
RRRR
EC' DC



[9] [10,11,12,13]Other ferrocenes of type B as well as B' and C' were synthesized later using
phosphaalkyne as starting material, the missing 1,2,3-triphosphaferrocene C was only recently
synthesized by Scherer and coworkers by treating the tetraphosphabicyclobutadiene complex
1 1 [14] [{Cp'''(CO) Fe} ( μ,η : η -P )] with diphenylacetylene.2 2 4
[15,16]An electrochemical investigation of the polyphosphaferrocenes shows that the
replacement of CR fragments by phosphorus atoms in the phospholyl ring enhances the
electron richness and thus increases the electron density at the iron center. This modification
made the phosphaferrocenes more difficult to oxidize.
Unlike the simple metallocene analogues, the complexes of phosphaferrocene have ligating
potential to transition metal centers with the ring phosphorus lone-pair electrons not only in π-
1 2ligation but also in η -or η -metal ligation.
1

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