Halfsandwich tungsten complexes with a silanol-functionalized cyclopentadienyl ligand [Elektronische Ressource] : synthesis and reactivity / vorgelegt von Holger Bera

Informations

• Publié par: julius-maximilians-universitat_wurzburg
• Publié le: 01 janvier 2005
• Nombre de lectures: 15
• Langue: Deutsch
• Poids de l'ouvrage: 4 Mo

Extrait

HALFSANDWICH TUNGSTEN COMPLEXES
WITH A SILANOL-FUNCTIONALIZED
CYCLOPENTADIENYL LIGAND

- SYNTHESIS AND REACTIVITY -


Dissertation zur Erlangung des naturwissenschaftlichen
Doktorgrades der Bayerischen Julius-Maximilians-
Universität Würzburg



Vorgelegt von

HOLGER BERA

aus Northeim



Würzburg 2005



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
Mai 2001 bis Dezember 2004
am Institut für Anorganische Chemie der Universität Würzburg
unter der Leitung von Prof. Dr. W. Malisch durchgeführt.



























Diese Arbeit ist meinen Eltern gewidmet.


CONTENTS


1 SCOPE.........................................................................................................

I SYNTHESIS AND REACTIVITY OF HALFSANDWICH
5TUNGSTEN COMPLEXES WITH A η -CYCLOPENTADIENYL-
23 BOUND SILANOL FUNCTION...............................................................

24 SUMMARY..................................................................................................

25 INTRODUCTION.........................................................................................

27 RESULTS AND DISCUSSION..................................................................
Li{W[(C H )SiMe H]L(CO) } [L = CO (2a), PMe (2b)]........................... 28 5 4 2 2 3
2a by reaction of Li[W(C H Li)(CO) ] (4) with Me Si(H)Cl....................... 29 5 4 3 2
[HMe Si(C H )](OC) WH (5) and [HMe Si(C H )](Me P)(OC) WR 2 5 4 3 2 5 4 3 2
[R = Me, SiMe H, SiMe (6a-c)]................................................................... 30 2 3
5 by reaction of HMe SiC H (7) with (MeCN) W(CO) ............................. 31 2 5 5 3 3
[ClMe Si(C R )](OC) WH [R = H (9a), Me (9b)]........................................ 32 2 5 4 3
[ClMe Si(C R )](OC) WCl [R = H (10a), Me (10b)]................................... 33 2 5 4 3
[HOMe Si(C H )](OC) WH (11).................................................................. 34 2 5 4 3
Synthesis of the tungsten-silanols 11, 13a-c.................................................. 35
O{[Me Si(C H )](OC) WCl} (14)............................................................... 36 2 5 4 3 2
X-ray diffraction analysis of [HOMe Si(C Me )](OC) WCl (13c)............... 37 2 5 4 3
Reactivity of tungsten-silanol 13b towards nBuLi........................................ 39
[HMe SiOMe Si(C H )](OC) WH (19)........................................................ 40 2 2 5 4 3
{[iBu AlOMe Si(C Me )](OC) WH} (20).................................................. 41 2 2 5 4 3 2
V Contents


42 CONCLUSION.............................................................................................

43 EXPERIMENTAL SECTION......................................................................
Crystal data for [HOMe Si(C Me )](OC) WCl (13c)................................... 57 2 5 4 3

59 REFERENCES..............................................................................................

63 TABLE OF COMPOUNDS...............................................................................

II HALFSANDWICH TUNGSTEN METHYL COMPLEXES WITH A
5 64 η -CYCLOPENTADIENYL-BOUND SILANOL FUNCTION....................

65 SUMMARY..................................................................................................

67 INTRODUCTION.........................................................................................

69 RESULTS AND DISCUSSION...................................................................
[ClR Si(C H )](OC) WMe [R = Me (3a), Ph (3b)] and 2 5 4 3
R Si[(C H )(OC) WMe] [R = Me (4a), Ph (4b)]......................................... 69 2 5 4 3 2
[HRR’Si(C H )](OC) WMe [R, R’ = Me, Ph, iPr (6a-d)]............................ 70 5 4 3
[ClR Si(C H )](OC) WMe [R = Me (3a), Ph (3b), iPr (7)], 2 5 4 3
[CliPr Si(C H )](OC) WCl (8) and {[CliPr Si(C H )](OC) W} (W-W) (9) 2 5 4 3 2 5 4 3 2
by reaction of 6a-c with PdCl ....................................................................... 71 2
7 by use of Li[W(C H Li)(CO) ] (11)........................................................... 73 5 4 3
[HOR Si(C H )](OC) WMe [R = Me, Ph, iPr (13a-c)]................................. 74 2 5 4 3
{[HOiPr Si(C H )](OC) W} (W-W) (14)..................................................... 75 2 5 4 3 2
O{[Me Si(C H )](OC) WMe} (15).............................................................. 76 2 5 4 3 2
[ROMe Si(C H )](OC) WMe [R = SiMe H (17a), SnMe (17b) and 2 5 4 3 2 3
Cp Ti(Cl) (17c)]............................................................................................. 77 2
{[iBu AlOMe Si(C H )](OC) WMe} (18).................................................. 78 2 2 5 4 3 2
VI Contents

Reaction cycle of 13a, [LiOMe Si(C H )](OC) WMe (19) and 2 5 4 3
[MeOMe Si(C H )](OC) WMe (20).............................................................. 79 2 5 4 3
X-RAY STRUCTURE DETERMINATIONS............................................................. 81
Ph Si[(C H )(OC) WMe] (4b)..................................................................... 81 2 5 4 3 2
[HPh Si(C H )](OC) WMe (6b).................................................................... 82 2 5 4 3
{[HOiPr Si(C H )](OC) W} (W-W) (14)..................................................... 84 2 5 4 3 2
Crystal data for 4b, 6b and 14........................................................................ 86

88 CONCLUSION.............................................................................................

89 EXPERIMENTAL SECTION......................................................................

105 REFERENCES..............................................................................................

110 TABLE OF COMPOUNDS...............................................................................

III PHOSPHINE-SUBSTITUTED TUNGSTEN COMPLEXES WITH
5 111 A η -CYCLOPENTADIENYL-BOUND SILANOL FUNCTION........

112 SUMMARY...................................................................................................

113 INTRODUCTION.........................................................................................

115 RESULTS AND DISCUSSION...................................................................
[XMe Si(C H )](OC) (Me P)WH [X = H (2a), Cl (2b)]............................. 115 2 5 4 2 3
[ClMe Si(C R )](OC) (Ph P)WCl [R = H (4a), Me (4b)] and 2 5 4 2 3
[CliPr Si(C H )](OC) (Ph P)WCl (4c).......................................................... 116 32 5 4 2
2 117 [ClMe Si(C H )](OC)(η -dppm)WCl (6)...................................................... 2 5 4
Synthesis of the tungsten-silanols 7a-c, 8 and 9............................................ 118
X-ray structure determinations of 7c and 8.................................................... 119
[HOMe Si(C Me )](OC) (Ph P)WCl (7c)..................................................... 120 2 5 4 2 3
VII Contents


[HOiPr Si(C H )](OC) (Ph P)WCl (8).......................................................... 122 2 5 4 2 3
Table of crystal data for 7c and 8................................................................... 123
[HMe SiOMe Si(C R )](OC) (Ph P)WCl [R = H (10a), Me (10b)]............. 124 2 2 5 4 2 3
O{[Me Si(C H )](OC) (Me P)WH} (11)..................................................... 125 2 5 4 2 3 2
X-ray structure determination of 11............................................................... 126
Table of crystal data for 11............................................................................ 128
2 130 [ROMe Si(C H )](OC)(η -dppm)WCl [R = HMe Si (13a), Me Sn (13b)].. 2 5 4 2 3

131 CONCLUSION.............................................................................................

132 EXPERIMENTAL SECTION......................................................................
1 29 29
Table 1 ( H- and Si-NMR values of silanols) and Table 2 ( Si-NMR
values of disiloxanes)..................................................................................... 144

145 REFERENCES..............................................................................................