Synthesis, reactions and properties of iron, cobalt and nickel complexes containing some (P,S)-chelating ligands and trimethylphosphine [Elektronische Ressource] / vorgelegt von Hamdi Bennour

H.-F. Klein

Informations

• Publié par: technischen_universitat_darmstadt
• Publié le: 01 janvier 2010
• Nombre de lectures: 20
• Langue: Deutsch
• Poids de l'ouvrage: 2 Mo

Extrait

Synthesis, Reactions, and Properties of
Iron, Cobalt, and Nickel Complexes Containing some
[P,S]-chelating Ligands and T rimethylphosphine

Vom Fachbereich Chemie
der Technischen Universität Darmstadt

zur Erlangung des akademischen Grades eines
Doktors rerum naturalium (Dr. rer. nat.)

genehmigte
Dissertation
vorgelegt von
M.Sc. Hamdi Bennour
aus Bengasi

Referent: Prof. Dr. H.-F. Klein
Korreferent : Prof. Dr. J. J. Schneider
Tag der Einreichung: 09. Dezember. 2009
Tag der mündlichen Prüfung: 08. Februar. 2010

Darmstadt 2010
D 17
Die vorliegende Arbeit wurde im Fachbereich Chemie der Technischen Universität Darmstadt,
Fachgebiet Anorganische Chemie, unter der Leitung von Prof. Dr. H.-F. Klein in der Zeit von
November 2003 bis Mai 2009 angefertigt.


Teile dieser Arbeit sind bereits veröffentlicht worden:
Synthesis and Properties of Molecular Nickel (II) Hydride, Methyl, and Nickel (I) Complexes
Supported by Trimethylphosphane and (2-Diphenylphosphanyl)-thiophenolato and naphtholato
Ligands. P. B. Kraikivskii, M. Frey, H. A. Bennour, A. Gembus, R. Hauptmann, I. Svoboda, H.
Fuess, V. V. Saraev, H.-F. Klein J. Organomet. Chem. 2009, 694, 1869-1876.













Ich danke allen Mitgliedern der Arbeitsgruppe Anorganische Chemie und besonders
Herrn Prof. Dr. H.-F. Klein für die wertvollen Anregungen und hilfreichen Diskussionen,
die zum Gelingen dieser Arbeit beigetragen haben













To my mother, my daughter
and
all the faithful of my friends around me
who gave me generous support and encouragement
during my PhD work













T A B L E O F C O N T E N TS


1 IN T R O DU C T I O N 1
1.1 The role of iron, cobalt and nickel complexes in organometallic catalysis 1
1.2 [P, S]-chelating ligands in complexes of transition metals 6
1.3 T rimethylphosphine as supporting ligand 10
1.4 Aims of the investigation at hand 10
2 R ESU L TS A ND DISC USSI O N 11
2.1 The prechelate systems (3-diphenylphosphino)-2-thionaphthol
and (2-diphenylphosphino)-(3-methylthio)naphthalene 11
2.2 Synthesis of (3-diphenylphosphino)-2-thionaphtholato-[P,S]-iron(II)
complexes 13
2.2.1 Synthesis of hydrido-{(3-diphenylphosphino)-2-thionaphtholato-[P, S]}
tris(trimethylphosphine)-iron(II) (1) 13
2.2.2 Reaction of complex 1 with carbon monoxide 17
2.2.3 Reaction of complex 1 with iodomethane 22
2.2.4 Reaction of Fe(CO) (PMe ) with(3-diphenylphosphino)-2-thionaphthol 25 2 3 3
2.2.5 Reaction of FeMe (PMe ) with (3-diphenylphosphino)-2-thionaphthol 26 2 3 4
2.3 Synthesis of chelate-[P, S]-cobalt complexes in oxidation states III and II 28
2.3.1 Preparation of hydrido-bis {(3-diphenylphosphino)-2-thiophenolato[P,S]} -
(trimethylphosphine)-cobalt (III) 28
2.3.2 Synthesis of trans-bis{(3-diphenylphosphino)-2-thiophenolato-[P,S]}-
(trimethylphosphine)-cobalt (II) 32
2.3.3. Synthesis of methyl{(3-diphenylphosphino)-2-thionaphtholato-[P, S]}-
bis(trimethylphosphine)-cobalt (II) 35
I Table of Contents
2.3.4 Synthesis of trans-bis{(3-diphenylphosphino)-2-thionaphtholato- [P,S]}-
cobalt (II) 37
2.3.5 Synthesis of hydrido-bis{(3-diphenylphosphino)-2-thionaphtholato-
[P, S]}- (trimethylphosphine)-cobalt (III) 40
2.3.6 Synthesis of trans-bis{(3-diphenylphosphino)-2-thionaphthato-[P, S]}-
(trimethylphosphine)-cobalt (II) 42
2.4 Synthesis of (3-diphenylphosphino)-2-thionaphtholato-[P, S]-nickel(II)
complexes 45
2.4.1 Synthesis of hydrido-(3-diphenylphosphino)-2-thionaphtholato-[P,S]-
bis(trimethylphosphine)-nickel(II) (12) 45
2.4.2 Reaction of 12 with 1.3-bis(diphenylphosphino) propane 49
2.4.3 Synthesis of methyl-(3-diphenylphosphino)-2-thionaphtholato-[P,S]-
nickel(II) complexes containing one and two trimethylphosphines 51

3 E XPE RI M E N T A L PA R T 58
3.1 Working techniques 58
3.2 Identification of compounds 58
3.2.1 Elemental analyses 58
3.2.2 X-ray diffraction crystallography 58
3.2.3 Infrared spectroscopy 59
3.2.4 Nuclear magnetic resonance spectroscopy 59
3.2.5 Melting and decomposition points 59
3.3 Preparation of educts 59
3.3.1 PMe 59 3
3.3.2 FeCl (PMe ) 60 2 3 2
3.3.3 FeMe (PMe ) 60 2 3 4
3.3.4 Fe(PMe ) 60 3 4
3.3.5 Co(PMe ) 60 3 4
3.3.6 CoMe(PMe ) 60 3 4
II Table of Contents
3.3.7 CoCl (PMe ) 61 2 3 3
3.3.8 CoMe (PMe ) 61 2 3 3
3.3.9 CoCl(PMe ) 61 3 3
3.3.10 NiCl (PMe ) 61 2 3 2
3.3.11 NiCl(Me)(PMe ) 61 3 2
3.3.12 NiMe (PMe ) 62 2 3 3
3.3.13 Ni(PMe ) 62 3 4
3.3.14 [NiMe(OMe)(PMe )] 62 3 2
3.4 [P, S]-ligand synthesis 62
3.4.1 (3-Diphenylphosphino)-2-thionaphthol 62
3.4.2 (2-Diphenylphosphino)-(3-methylthio)naphthalene 64
3.4.3 (2-Diphenylphosphino)-thiophenol 65
3.5 Synthesis of new complexes 66
3.5.1 General procedure A for iron complexes 66
3.5.2 General procedure B for cobalt complexes 67
3.5.3 General procedure C for iron complexes 67
3.5.4 General procedure D for reactions under carbon monoxide 67
3.5.5 General procedure E for reactions with iodomethane 67
3.6 New complexes 68
3.6.1 Hydrido-[(3-diphenylphosphino)-2-thionaphtholato]-[P,S]
tris(trimethylphosphine)-iron(II) (1) 68
3.6.2 Hydrido-[(3-diphenylphosphino)-2-thionaphtholato]- [P,S]
(carbonyl)-bis(trimethylphosphine)-iron(II) (2) 70
3.6.3 [(3-Diphenylphosphino)-2-thionaphtholato] [P,S]-iodo-
tris(trimethylphosphine)-iron(II) (3) 71
3.6.4 Bis[(3-diphenylphosphino)-2-thionaphtholato]-[P,S]-(carbonyl)-
(trimethylphosphine)-iron(II) (4) 73
3.6.5 trans-Bis{(3-diphenylphosphino)-2-thionaphtholato-[P,S]}-(carbonyl)-
(trimethylphosphine)-iron(II) (5) 74
III Table of Contents

3.6.6 Hydrido-bis{(2-diphenylphosphino)-thiophenolato-[P,S]}-
(trimethylphosphine)-cobalt(III) (6) 75
3.6.7 trans-Bis{(2-diphenylphosphino)-thiophenolato-[P,S]}-
(trimethylphosphine)-cobalt(II) (7) 77
3.6.8 Methyl{(3-diphenylphosphino)-2-thionaphtholato-[P,S]}-bis
(trimethylphosphine)-cobalt(II) (8) 78
3.6.9 trans-Bis{(3-diphenylphosphino)-2-thionaphtholato-[P,S]}-cobalt(II) (9) 79
3.6.10 Hydrido-bis{(3-diphenylphosphino)-2-thionaphtholato-[P,S]}-
(trimethylphosphine)-cobalt(III) (10) 80
3.6.11 trans-Bis{(3-diphenylphosphino)-2-thionaphtholato-[P,S]}-
(trimethylphosphine)-cobalt(II) (11) 82
3.6.12 Hydrido-{(3-diphenylphosphino)-2-thionaphtholato-[P,S]}-bis
(trimethylphosphine)-nickel(II) (12) 83
3.6.13 Hydrido-(3-diphenylphosphino)-2-thionaphtholato-[P,S]-
[bis(diphenylphosphino)propane]nickel(II) (13) 84
3.6.14 trans-Methyl{(3-diphenylphosphino)-2-thionaphtholato-[P,S]}-
(trimethylphosphine)-nickel(II) (14) 86
3.6.15 Methyl-{(3-diphenylphosphino)-2-thionaphtholato-[P,S]}-bis
(trimethylphosphine)-nickel(II) (15) 87
4 SU M M A R Y 90
5 Z USA M M E N F ASSUN G 97
6 R E F F E R E N C ES 104
7 D A N K