Hendrik Dorn

Rhodium‐katalysierte Bildung von Phosphor‐Bor‐Bindungen: Synthese des ersten Poly(phosphanylborans) mit hoher Molekülmasse

EinanorganischesAnalogondesPolystyrols ist Poly(phenylphosphanylboran), und es ist das erste gut charakterisierte Polymer mit hoher Molekulmasse, das ein Ruckgrat aus alternierenden Phosphor- und Boratomen enthalt. Es ist uber die metallkatalysierte „Dehydrokupplung” eines primaren Phosphan-Boran-Addukts zuganglich (siehe Schema).

Supramolecular Organometallic Polymer Chemistry: Self-Assembly of a Novel Poly(ferrocene)-b-polysiloxane-b-poly(ferrocene) Triblock Copolymer in Solution.

Micelles with unprecedented flowerlike arrangements of the poly(ferrocene) cores (shown in the TEM image) are among the supramolecular architectures generated in the self-assembly of a novel organometallic triblock copolymer from silicon-bridged [1]ferrocenophane monomers and [Me(2)SiO](3) in hexane, a solvent selective for the central polysiloxane block.

ORGANOMETALLIC FLUORIDES OF THE LANTHANIDE AND ACTINIDE ELEMENTS

Abstract A brief survey of the preparation, and chemical and structural properties of organolanthanide and actinide fluoride complexes is given.

New Inorganic Polymers Containing Phosphorus

The relatively unexplored area of main group polymer chemistry continues to offer fertile ground for scientific study. In this chapter recent developments in the area of linear inorganic polymers based on phosphorus are reviewed. The 1990s saw the development of a number hybrid polymer systems where elements such as carbon and sulfur were incorporated into polymer backbones along with phosphorus and nitrogen. Many of these novel materials were synthesized via the ring-opening polymerization of cyclic heterophosphazenes. Polythionylphosphazenes, hybrids of “classical” polyphosphazenes and polyoxothiazenes, are discussed in particular detail. In addition, polyphosphinoboranes, with a main chain comprising alternating phosphorus and boron atoms, have been recently prepared via the transition metal catalyzed dehydrocoupling of phosphine-borane adducts. These novel materials are also described.

Supramolekulare metallorganische Polymerchemie: Selbstorganisation des neuartigen Dreiblockcopolymers Poly(ferrocen)‐b‐polysiloxan‐b‐poly(ferrocen) in Lösung

Micellen mit blutenformigen Anordnungen der Poly(ferrocen)-Kerne (siehe TEM-Aufnahme) sind nur eines der supramolekularen Gebilde, die bei der Selbstorganisation der Titelverbindung in Hexan, einem fur den zentralen Polysiloxanblock selektiven Losungsmittel, entstehen. Das metallorganische Dreiblockcopolymer wurde aus siliciumverbruckten [1]Ferrocenophanmonomeren und [Me2SiO]3 erhalten.

Derivatives of Group 4 metal amide chlorides and fluorides: synthesis, structure and characterization of novel dimethyl and fluoro–chloro complexes

Reaction of MgMeBr with [MCl2L2] and [MCl2(η-C5Me5)L][L =(2,6-Pri2C6H3)N(SiMe3), M = Zr or Hf] gave the corresponding dimethyl complexes [MMe2L2](M = Zr 1a or Hf 1b) and [MMe2(η-C5Me5)L](M = Zr 2a or Hf 2b). Reaction of [ZrF2L2] with AlMe3 also yielded 1a. The structures of 1a and 2a have been determined by single-crystal X-ray crystallography. Upon reaction of 1 molar equivalent of SnMe3F with [MCl2L2] and [MCl2(η-C5Me5)L] mixed fluoro–chloro complexes, [MCl(F)L2](M = Zr 3a or Hf 3b) and [MCl(F)(η-C5Me5)L](M = Zr 4a or Hf 4b) were formed, via elimination of SnMe3Cl. The structure of 4a has been determined by single-crystal X-ray analysis.

Synthesis and catalytic properties of novel zirconium fluoro-sulfonato and bis(sulfonate) complexes: crystal structure of [(η5-C5Me5)2Zr(OSO2CF3)2]

Abstract Treatment of [( η 5 -C 5 Me 5 ) 2 ZrF 2 ] with Me 3 SiOSO 2 R (R = CF 3 , C 6 H 4 - p -CH 3 ) yield both the monosubstituted [( η 5 -C 5 Me 5 ) 2 ZrF(OSO 2 R)] ( 1 , R = CF 3 ; 2 , R = C 6 H 4 - p -CH 3 ) and disubstituted [( η -C 5 Me 5 ) 2 Zr(OSO 2 R) 2 ] ( 3 , R = CF 3 ; 4 , R = C 6 H 4 - p -CH 3 ) sulfonate complexes, when using stoichiometric amounts of reagents. An X-ray diffraction study of 3 revealed that the trifluoromethanesulfonate ligands are covalently bound to zirconium. Compounds 1–4 along with [( η 5 -C 5 Me 5 ) 2 ZrF(OCOCF 3 )] (5) and [( η 5 -C 5 Me 5 ) 2 Zr(OCOCF 3 ) 2 ] (6) were investigated as catalysts for the polymerization of ethylene in combination with methylaluminoxane (MAO).

Transition Metal-Catalyzed Formation of Phosphorus-Boron Bonds: a New Route to Phosphinoborane Rings, Chains and the First High Polymers

A novel catalytic route for the formation of phosphorus-boron bonds has been developed. The dehydrogenative coupling of the phosphine-borane adducts Ph2PH·BH3 and PhPH2·BH3 is efficiently catalyzed by transition metal-complexes such as [Rh(1,5-cod)2][OTf] or [{Rh(μ-Cl)(1,5-cod)}2] to give the linear compound HPPh2-BH2-PPh2-BH3 (1), the cyclic phosphinoboranes [Ph2P-BH2]3(2a) and [Ph2P-BH2]4 (2b), and the first high molecular weight poly(phosphinoborane) [PhPH-BH2]n (3).

Diethyl­ammonium di­phenyl­phosphinate

In the title compound, C4H12N+·C12H10O2P−, the Et2NH2+ and Ph2PO2− moieties in the asymmetric unit are linked by P—O⋯H—N hydrogen bonds [O⋯N distance 2.6722 (15) A]. These hydrogen-bonded pairs are in turn linked by intermolecular P—O⋯H—N hydrogen bonds [O⋯N distance 2.6943 (15) A] to form infinite chains along 21 screw axes in the y direction.

Synthesis and novel reactivity of platinum phosphine–borane complexes trans-[PtH(PPhR·BH3)(PEt3)2] (R = H, Ph)

The oxidative-addition reaction of Pt(PEt3)3 with the phosphine–borane adducts PhPH2·BH3 and Ph2PH·BH3 leads to regioselective insertion of the Pt(PEt3)2 fragment into the P–H bond to afford the hydride complexes trans-[PtH(PPhR·BH3)(PEt3)2 ] (R = H 1, R = Ph 2); reaction of 2 with PhPH2·BH3 leads to an unusual ligand exchange reaction which generates 1 and Ph2PH·BH3.