Reactivity of Lewis Base Stabilized Pnictogenylboranes Towards Transition Metal Complexes

URN to cite this document:: urn:nbn:de:bvb:355-epub-383901
DOI to cite this document:: 10.5283/epub.38390

Braese, Jens

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Date of publication of this fulltext: 10 Jan 2020 06:40

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Item type:	Thesis of the University of Regensburg (PhD)
Date:	10 January 2020
Referee:	Prof. Dr. Manfred Scheer
Date of exam:	11 January 2019
Institutions:	Chemistry and Pharmacy > Institut für Anorganische Chemie > Chair Prof. Dr. Manfred Scheer
Keywords:	phosphorus, boron, group 13 15, transition metal complexes, inorganic polymers, catalysis, polymerization, aurophilicity, luminescence
Dewey Decimal Classification:	500 Science > 540 Chemistry & allied sciences
Status:	Published
Refereed:	Yes, this version has been refereed
Created at the University of Regensburg:	Yes
Item ID:	38390

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Abstract (English)

Abstract (English)

The reactivity of Lewis base stabilized pnictogenylboranes towards transition metal complexes has been investigated.

Reaction of Lewis base stabilized phosphinoborane monomer tBuHPBH2NMe3 with catalytic amounts of bis(η5:η1-adamantylidenepentafulvene)titanium provide a convenient new route to polyphosphinoboranes [tBuPH-BH2]n. This method offers access to high molecular mass materials under mild conditions and short reaction times. It represents an unprecedented example of a transition-metal mediated polymerization of Lewis base stabilized Group 13/15 compounds. For this reaction a variety of different monomers of the type RR’EBH2NMe3 (E = P, As; R/R’ = H, alkyl, aryl) has been tested.

The structural and photophysical properties of a series of new Au(I) compounds have been studied. The reactions of AuCl(tht) with the phosphanyl- and arsanylboranes RR’EBH2NMe3 (E = P, As; R = H, Ph; R’ = H, Ph, tBu) afford the complexes [AuCl(RR’EBH2NMe3)]. In the solid state, [AuCl(H2PBH2NMe3)]2 is a dimer showing unsupported intermolecular aurophilic interactions with short Au…Au distances. In contrast, [AuCl(H2AsBH2NMe3)]n aggregates to form 1D chains. Organic substituents on the pnictogen atoms lead to discrete molecules in [AuCl(RR’PBH2NMe3)] (R = H, R’ = tBu or R = R’ = Ph). To increase the aurophilicity, the ionic homoleptic complexes [Au(RR’EBH2NMe3)2][AlCl4] have been synthesized for which 3a,b form chains in the solid state and exhibit luminescence. The emissions show a drastic redshift with temperature decrease correlating with decreasing Au...Au distances. DFT calculations provide insight into the bonding situation of the products.

Reactions of the pnictogenylboranes H2EBH2·NMe3 (E = P, As) and Ph2PBH2·NMe3 with [Cu(MeCN)4][BF4] afford the homoleptic complexes [Cu(H2EBH2·NMe3)4(BF4)] (E = P, As) and [Cu(Ph2PBH2·NMe3)3][BF4]. Compound [Cu(H2AsBH2·NMe3)4(BF4)] represents the first structurally characterized complex of a primary arsine coordinated to a Cu center. From reactions of Ph2PBH2·NMe3 with CuX, a series of 10 complexes [CunXn(Ph2PBH2·NMe3)m] (X = Cl, Br, I; n = 1-6, m = 2-4) were synthesized and compared to related complexes possessing Ph3P ligands. All complexes were characterized by single-crystal X-ray structure analysis, multinuclear NMR spectroscopy, IR spectroscopy and mass spectrometry.