Investigations into tin- and tantalum-phosphorus compounds for low-coordinate moieties and supramolecular assemblies [Elektronische Ressource] / vorgelegt von Brian P. Johnson
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Investigations into tin- and tantalum-phosphorus compounds for low-coordinate moieties and supramolecular assemblies [Elektronische Ressource] / vorgelegt von Brian P. Johnson

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Investigations into Tin- and Tantalum-Phosphorus Compounds for Low-Coordinate Moieties and Supramolecular Assemblies Dissertation zur Erlangung des Doktorgrades der Naturwissenschaften (Dr. rer. nat.) der Naturwissenschaftlichen Fakultät IV – Chemie und Pharmazie der Universität Regensburg vorgelegt von Brian P. Johnson aus Gallatin, Tennessee, USA 2005 Promotionsgesuch eingereicht am: 05. Dezember 2005 Die Arbeit wurde angeleitet von: Prof. Dr. M. Scheer Vorsitzender: Prof. Dr. R. Winter Prüfungsausschuß: (1. Gutachter) Prof. Dr. H. Brunner (2. Gutachter) B. König (3. Prüfer) Tag der Promotion: 11. Januar 2006Dedicated to my family Die vorliegende Arbeit wurde in der Zeit von September 2001 bis März 2004 am Institut für Anorganische Chemie der Universität Karlsruhe (TH) sowie in der Zeit von April 2004 bis November 2005 am Institut für Anorganische Chemie der Universität Regensburg unter Anleitung von Herrn Prof. Dr. M. Scheer angefertigt. Table of Contents i 1 Introduction 1 1.1 Phosphanyl compounds in main-group chemistry 21.1.1 Phosphanyl stannylenes 31.1.2 Multiple bonding in tin-phosphorus compounds 61.2 Stabilization of low-coordinate moieties with bulky terphenyl ligands 81.3 Novel phosphorus ligands in transition-metal complexes 101.3.

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Published 01 January 2006
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Investigations into Tin- and Tantalum-Phosphorus Compounds
for Low-Coordinate Moieties and Supramolecular Assemblies




Dissertation zur Erlangung des
Doktorgrades der Naturwissenschaften (Dr. rer. nat.)

der Naturwissenschaftlichen Fakultät IV – Chemie und Pharmazie
der Universität Regensburg










vorgelegt von
Brian P. Johnson
aus Gallatin, Tennessee, USA
2005

























Promotionsgesuch eingereicht am: 05. Dezember 2005
Die Arbeit wurde angeleitet von: Prof. Dr. M. Scheer
Vorsitzender: Prof. Dr. R. Winter
Prüfungsausschuß: (1. Gutachter)
Prof. Dr. H. Brunner (2. Gutachter) B. König (3. Prüfer)

Tag der Promotion: 11. Januar 2006Dedicated to my family




























Die vorliegende Arbeit wurde in der Zeit von September 2001 bis März 2004 am Institut für
Anorganische Chemie der Universität Karlsruhe (TH) sowie in der Zeit von April 2004 bis
November 2005 am Institut für Anorganische Chemie der Universität Regensburg unter
Anleitung von Herrn Prof. Dr. M. Scheer angefertigt.
Table of Contents i


1 Introduction 1

1.1 Phosphanyl compounds in main-group chemistry 2
1.1.1 Phosphanyl stannylenes 3
1.1.2 Multiple bonding in tin-phosphorus compounds 6
1.2 Stabilization of low-coordinate moieties with bulky terphenyl ligands 8
1.3 Novel phosphorus ligands in transition-metal complexes 10
1.3.1 Transition-metal phosphinidene complexes 11
1.3.2 P -ligand complexes 12n
1.4 Supramolecular chemistry of P -ligand complexes 12n
1.4.1 Polymeric networks 13
1.4.2 Fullerene-like 3D structures 14

2 Research Objectives 16


3 Results and Discussion 17

3.1 Stabilization of Sn/P compounds by transition-metal fragments 17
3.1.1 Background and research objective 17
3.1.2 Reactions of SnCl and Sn[N(SiMe ) ] with Li[H PW(CO)] and 182 3 2 2 2 5
[H PW(CO) ] 3 5
F3.1.3 Reaction of [(CO) WSnCl (thf) ] with Li[H PBAr] 195 2 2 2 3
3.1.4 Synthesis of [H(Me Si) PW(CO) ] (2) 203 2 5
3.1.5 Reactions of SnCl and Sn[N(SiMe ) ] with Li[(Me Si) PW(CO) ] and 212 3 2 2 3 2 5
[H(Me Si) PW(CO) ] 3 2 5
3.1.6 Reaction of [Fp SnX ] (X = Cl, Br) with Li[H PW(CO)] 232 2 2 5
3.1.7 Reaction of [Fp SnBr ] with LiP(SiMe )·1.8THF 292 2 3 2
3.1.8 Reaction of [Fp SnCl ] with LiP(H)Trip 322 2
3.2 Investigations into tin-phosphorus compounds supported by bulky aryl 36
groups
3.2.1 Background and research objective 36
3.2.2 Preparation of Ph*SnCl 37ii Table of Contents
3.2.3 Reactions of Ph*SnCl with alkali-metal phosphanides 38
3.2.3.1 Synthesis of Ph*SnP(SiMe ) (7) 383 2
3.2.3.2 Reactivity of Ph*SnP(SiMe ) (7) 443 2
3.2.3.3 Reactions of Ph*SnCl with LiP(H)Ph, LiP(H)Trip, and LiPTrip 452
3.2.3.4 Reaction of Ph*SnCl with Li[H PW(CO)] 502 5
3.2.4 Reactions of Ph*SnCl with PCl and Cp*PCl 543 2
3.2.5 Oxidation of Ph*SnCl with Me SiOOSiMe and MeNO 563 3 3
3.2.5.1 Synthesis of Ph*Sn(OSiMe ) Cl (12) 563 2
3.2.5.2 56 [Ph*Sn(µ-O)Cl] (13) 2
3.2.6 Synthesis of Ph*SnCl (14a) 593
3.2.7 62Reactions of (14a), Ph*Sn(OSiMe ) Cl (12), and [Ph*Sn(µ-O)Cl] 3 3 2 2
-(13) with [P(SiMe ) ] 3 2
3.3 Tris(aryloxy)amine tantalum complex for probing reactivity with 64
phosphanide reagents
3.3.1 Background and research objective 64
3.3.2 Synthesis of [L*TaCl ] (15) 652
3.3.2.1 Route via lithiation of L*H 653
3.3.2.2 Direct thermolysis of L*H with TaCl 663 5
3.3.3 Synthesis of [L*Ta(Cl)E(SiMe ) ] (E = P (16a), As(16b)) 703 2
3.3.4 [L*TaMe ] (17) 752
3.4 cyclo-P tantalum complex for formation of supramolecular assemblies 794
3.4.1 Background and research objective 79
43.4.2 80Preparation of [Cp’’Ta(CO) (η -P )] (18) 2 4
4 1 1 1 13.4.3 Synthesis of [{Cp’’Ta(CO) (µ,η :η :η :η :η -P )} {CuCl} ] (19a) 812 4 6 8
4 1 1 1 13.4.4 (µ,η :η :η :η :η -P )} {CuBr} ] (19b) 902 4 6 8
43.4.5 94Reaction of [Cp’’Ta(CO) (η -P )] (18) with CuI 2 4

4 Experimental Section 96

4.1 General remarks 96
4.1.1 Methods 96
4.1.2 Spectroscopy and analysis 96
4.2 Starting materials 97
4.2.1 Synthesis of [H(Me Si) PW(CO) ] (2) 973 2 5Table of Contents iii
4.2.2 Synthesis of 2,6-dichloro-1-iodobenzene 98
4.2.3 Ph*I 99
4.2.4 Synthesis of Ph*Li·OEt 1002
4.2.5 Ph*SnCl 101
4.3 Reactions starting from SnCl and Sn[N(SiMe ) ] 1022 3 2 2
4.3.1 Reaction of Sn[N(SiMe ) ] with [H(Me Si) PW(CO) ], isolation of 1023 2 2 3 2 5
[(Me Si) PW(CO) ] (3) 3 3 5
4.3.2 Reaction of SnCl with Li[(Me Si) PW(CO) ], isolation of 1022 3 2 5
[(Me Si) PW(CO) ] (3) 3 3 5
4.4 Reactions starting from [Fp SnX ] (X = Cl, Br) 1022 2
4.4.1 Synthesis of [Fp Sn{PH W(CO) } ] (4) 1022 2 5 2
4.4.2 [Fp Sn{P(SiMe ) } ] (5) 1032 3 2 2
4.4.3 Reaction of [Fp SnCl ] with LiP(H)Trip in THF, synthesis of Fp Sn (6) 1042 2 4
4.5 Reactions starting from Ph*SnCl 105
4.5.1 Synthesis of Ph*SnP(SiMe ) (7) 1053 2
4.5.2 Reaction of Ph* SnP(SiMe ) with BrCH CH Br, formation of Ph*Br (8) 1063 2 2 2
4.5.3 Reaction of Ph*SnCl with LiP(H)Ph (2 equivalents) 106
4.5.4 Reaction of Ph*SnCl with LiP(H)Ph (1 equivalent) 106
4.5.5 Reaction of Ph*SnCl with LiP(H)Trip, generation of Ph*SnP(H)Trip (9) 107
+ -4.5.6 PTrip, generation of Li [Ph*SnPTrip] (10, 1072
proposed)
4.5.7 Reaction of Ph*SnCl with Li[H PW(CO) ], formation of 1082 5
[Ph*Sn{W(CO) }(µ-O) SnPh*] (11) 5 2
4.5.8 Reaction of Ph*SnCl with Cp*PCl 1082
4.5.9 Synthesis of Ph*Sn(OSiMe ) Cl (12) 1093 2
4.5.10 109 [Ph*Sn(µ-O)Cl] (13) 2
4.6 Reactions involving Ph*Sn(IV)-halides and pseudohalides 110
4.6.1 Synthesis of Ph*SnCl (14a) 1103
4.6.2 Ph*SnBr (14b) 1113
4.6.3 112Reaction of Ph*SnCl , Ph*Sn(OSiMe ) Cl, and [Ph*Sn(µ-O)Cl] with 3 3 2 2
LiP(SiMe ) ·1.8THF 3 2
4.7 Reactions involving tris(aryloxy)amine (L*) 112
4.7.1 Synthesis of Li L* 1123
4.7.2 [L*TaCl ] (15) 1132iv Table of Contents
4.7.3 Synthesis of [L*Ta(Cl)P(SiMe ) ] (16a) and [L*Ta(Cl)As(SiMe ) ] (16b) 1143 2 3 2
4.7.4 [L*TaMe ] (17) 1152
44.8 116Reactions involving [Cp’’Ta(CO) (η -P )] 2 4
4.8.1 Synthesis of Cp’’H 116
4.8.2 Preparation of Cp’’Sn(nBu) 1163
4.8.3 Preparation of [Cp’’TaCl] 1164
4.8.4 Preparation of [Cp’’Ta(CO)] 1174
44.8.5 117Preparation of [Cp’’Ta(CO) (η -P )] (18) 2 4
4 1 1 1 14.8.6 118Preparation of [{Cp’’Ta(CO) (µ,η :η :η :η :η -P )} {CuX} ] (X = Cl (19a), 2 4 6 8
Br (19b), I (proposed, 19c))

5 Crystallographic Data 120

5.1 General remarks 120
5.2 [(Me Si) PW(CO) ] (3) 1223 3 5
5.3 [Fp Sn{H PW(CO) } ] (4) 1252 2 5 2
5.4 [Fp Sn{P(SiMe ) } ] (5) 1282 3 2 2
5.5 [Fp Sn] (6) 1314
5.6 Ph*SnP(SiMe ) (7) 1343 2
5.7 137[Ph*Sn{W(CO) }(µ-O)SnPh*] (11) 5
5.8 140[Ph*Sn(µ-O)Cl] (13) 2
5.9 Ph*SnCl (14a) 1433
5.10 [L*TaCl ] (15) 1462
5.11 [L*Ta(Cl)P(SiMe ) ] (16a) 1493 2
5.12 [L*Ta(Cl)As(SiMe ) ] (16b) 1523 2
5.13 [L*TaMe ] (17) 1552
4 1 1 1 15.14 [{Cp’’Ta(CO) (µ,η :η :η :η :η -P )} {CuCl} ] (19a) 1582 4 6 8
4 1 1 1 15.15 (µ,η :η :η :η :η -P )} {CuBr} ] (19b) 1612 4 6 8

6 Conclusion 168

6.1 Transition-metal supported tin-phosphorus compounds 168
6.2 Kinetically stabilized low-coordinate tin-phosphorus compounds 169
6.3 Survey of a tris(aryloxy)amine tantalum platform 171
6.4 Use of a cyclo-P tantalum complex for synthesis of spherical molecules 1724Table of Contents v

7 Appendices 174

A.1 Directory of abbreviations 174
A.1.1 NMR abbreviations 176
A.1.2 IR abbreviations 176
A.2 Directory of compounds 176
A.3 Literature cited 178