Neue Untersuchungen zum Reaktionsverhalten von Triorganylcyclotriphosphanen. Die Kristallstrukturen von [(PPh3)2Pt(PtBu)3], [(PPh3)2Pd(PtBu)2], [(CO)4Cr{(PiPr)3}2], [RhCl(PPh3)(PtBu)3], [(NiCO)6(μ2-CO)3{(PtBu)2}2] und [(CpFeCO)2(μ-CO)(μ-PHtBu)]+ · [FeCl3(thf)]–

Abstract

Bei der Umsetzung von Triorganylcyclotriphosphanen mit Übergangsmetallkomplexen entstehen ein‐ und mehrkernige Verbindungen, in denen die Cyclophosphane in unterschiedlicher Form – teils unter Erhalt ihrer Ringstruktur, teils unter Ringöffnung – an das Metall binden. Durch weitere Ligandabspaltung kann man zu größeren Aggregaten gelangen. Abhängig von den Reaktionsbedingungen konnten folgende Verbindungen charakterisiert werden:[(PPh3)2Pt(PtBu)3] (1), [(PPh3)2Pd(PtBu)2] (2), [(CO)4Cr{(PiPr)3}2] (3), [RhCl(PPh3)(PtBu)3] (4), [(NiCO)6(μ2‐CO)3{(PtBu)2}2] (5) und [(CpFeCO)2(μ‐CO)(μ‐PHtBu)]+ · [FeCl3(thf)]– (6). Die Strukturen von 1–6 wurden mit Hilfe der Einkristall‐Röntgenstrukturanalyse aufgeklärt (1: Raumgruppe P21/n (Nr. 14), Z = 4, a = 1279,6(3) pm, b = 1733,1(4) pm, c = 2079,1(4) pm, β = 90,20(3)°; 2: Raumgruppe P21/c (Nr. 14), Z = 4, a = 1053,3(2) pm, b = 2085,2(4) pm, c = 1855,7(4) pm, β = 98,77(3)°; 3: Raumgruppe P 1 (Nr. 2), Z = 2, a = 1022,6(2) pm, b = 1026,4(2) pm, c = 1706,0(3) pm, α = 82,36(3)°, β = 86,10(3)°, γ = 64,40(3)°; 4: Raumgruppe P 1 (Nr. 2), Z = 2, a = 980,2(2) pm, b = 1309,5(3) pm, c = 1573,4(3) pm, α = 99,09(3)°, β = 99,46(3)°, γ = 111,87(3)°; 5: Raumgruppe P21/c (Nr. 14), Z = 4, a = 1804,0(5) pm, b = 2261,2(6) pm, c = 1830,1(7) pm, β = 96,99(3)°; 6: Raumgruppe P21/c (Nr. 14), Z = 4, a = 943,2(3) pm, b = 2510,6(7) pm, c = 1325,1(6) pm, β = 98,21(3)°).

Synthesis of μ-Phosphido Diiron Complexes Having a P−H Bond: Hydrophosphination of Phenylacetylene and Methyl Acrylate with the Cationic μ-Phosphido Diiron Complex

“…On consideration of the steric repulsion among two Cp rings and a phenyl group on the μ-phosphido ligand, the cis (H) type geometry in Chart is preferred to the cis (Ph) type one. A similar cis -configuration is also found in a closely related cationic complex [Cp 2 Fe 2 (CO) 2 (μ-CO)(μ-PH t Bu)][FeCl 3 (THF)], reported by Fenske et al Apparently, by replacing the bridging hydrido ligand in 1a with a bridging carbonyl ligand to form 2 , the geometry changed drastically from trans to cis . This may be attributable to the much larger steric requirement of the μ-CO in 2 compared to that of the μ-H in 1a .…”

Making and Breaking of P–P Bonds with Low‐Valent Transition‐Metal Complexes

“…The chemistry of tetraaryltetraphosphane‐1,4‐diides(P 4 R 4 ) 2– has proved to be as intriguing as that of alkali‐metal cyclo ‐oligophosphanides 3. Thus, in addition to the previously known group 4,4 nickel,5 and platinum6 oligophosphanide complexes, we have observed that the dianions (P 4 R 4 ) 2– (R = Ph or Mes; Mes = 2,4,6‐Me 3 C 6 H 2 ) remain intact in transmetallation reactions with late‐transition‐metal halides such as [CuCl(PCyp 3 ) 2 ] (Cyp = cyclo ‐C 5 H 9 ) to give [Cu 4 (P 4 Ph 4 ) 2 (PCyp 3 ) 3 ]2a or with [PtCl 2 (L) 2 ] to give complexes of the type [Pt(P 4 Mes 4 ) 2 (L) 2 ] [(L) 2 = cod, dppe; L = C≡N t Bu, and C≡NCy; cod = 1,5‐cyclooctadiene, dppe = Ph 2 PCH 2 CH 2 PPh 2 , and Cy = cyclo ‐C 6 H 11 ] 2g. In addition, in the reaction of Na 2 (P 4 Ph 4 ) with [Cp*TaCl 4 ] (Cp* = C 5 Me 5 ) tantalum was apparently reduced by the dianion, and subsequent rearrangement and oxidativeaddition gave the (phosphinidene)tantalum(V) complex [Cp*Ta(Ph)(P 6 Ph 5 )] 2b.…”

The Main Group Macrocycle [{(PCH2CH2PAlMe2)2}4]⋅4 [AlMe3]

“…The work of Scherer, Driess, Fenske, and others2, 5, 6 concerning the studies of substituent‐free phosphorus–metal complexes,7 is one example where studies have crossed these disciplinary lines. These disciplinary boundaries have been further eroded with the studies of phosphanide and phosphanediyl clusters reported by the research groups of Fenske8–11 and Driess 12–14. While these systems employ phosphorus atoms to link metals in complex clusters, we have targeted systems in which chains of phosphorus atoms act as metal‐linking units.…”