Neue Phosphor‐verbrückte Übergangsmetall‐Komplexe Die Kristallstrukturen von [Co₄(CO)₁₀(PⁱPr)₂], [Fe₃(CO)₉(P^tBu)(PPh)], [Cp₃Fe₃(CO)₂(PP^tBu)(P^tBu)], [(NiPPh₃)₂(PⁱPr)₆], [(NiPPh₃)Ni{(P^tBu)₃}₂] und [Ni₈(P^tBu)₆(PPh₃)₂]

Abstract

Bei der Umsetzung von Cyclophosphanen mit Übergangsmetallcarbonylderivaten entstehen mehrkernige Komplexe, in denen die PR‐Liganden (R = organische Gruppe) in unterschiedlicher Form an das Metall gebunden sind. Abhängig von den Reaktionsbedingungen konnten folgende Verbindungen charakterisiert werden: [Co4(CO)10(PiPr)2] (2), [Fe3(CO)9 · (PtBu)(PPh)] (3), [Cp3Fe3(CO)2(PPtBu)(PtBu)] (4), [(NiPPh3)2 · (PiPr)6] (5), [(NiPPh3)Ni{(PtBu)3}2] (6) und [Ni8(PtBu)6(PPh3)2] (7). Die Strukturen von 2 – 7 konnten durch Einkristall‐Röntgenstrukturanalyse aufgeklärt werden (2: Raumgruppe Pccn (Nr. 56), Z = 4, a = 1001,4(2) pm, b = 1375,1(3) pm, c = 1675,5(3) pm; 3: Raumgruppe P21 (Nr. 4), Z = 2, a = 914,3(4) pm, b = 1268,7(4) pm, c = 1028,2(5) pm, β = 101,73(2)°; 4: Raumgruppe P1 (Nr. 2), Z = 2, a = 946,0(5) pm, b = 1074,4(8) pm, c = 1477,7(1,0) pm, α = 107,63(5)°, β = 94,66(5)° γ = 111,04(5)°; 5: Raumgruppe P1 (Nr. 2), Z = 2, a = 1213,6(2) pm, b = 1275,0(2) pm, c = 2038,8(4) pm, α = 92,810(10)°, β = 102,75(2)°, γ = 93,380(10)°; 6: Raumgruppe P1 (Nr. 2), Z = 2, a = 1157,5(5) pm, b = 1371,9(6) pm, c = 1827,6(10) pm; α = 69,68(3)°, β = 80,79(3)°, γ = 69,36(3)°; 7: Raumgruppe P3 (Nr. 147), Z = 1, a = 1114,1(2) pm, b = 1114,1(2) pm, c = 1709,4(3) pm).

Mild P–P Bond Cleavage in the Methyldiphosphenyl Complex [Mo2Cp2(μ-PCy2)(μ-κ2:κ2-P2Me)(CO)2] To Give Novel Phosphide-Bridged Trinuclear Derivatives

“…Alternatively, the terminal complex can bind a second metal fragment through its P–P double bond to give a P : P , P ′-bridged derivative (type C coordination), as observed in the reaction of [FeCp*(CO) 2 (κ 1 -P 2 Mes*)] with a Pt(PPh 3 ) 2 moiety to give [FePtCp*(μ-κ 1 :κ 2 -P 2 Mes*)(CO) 2 (PPh 3 ) 2 ] . Finally, a few examples of the μ 3 -P 2 R complexes have been also reported, these involving the participation of both P-based LPs and also the P–P double bond for binding to the metal atoms, as found in the triiron complexes [Fe 3 Cp 3 (CO) 2 (μ 3 -κ 1 :κ 2 :κ 1 -P 2 t Bu)(μ 3 -P t Bu)] (type E), [Fe 3 Cp*(μ 3 -κ 1 :κ 1 :κ 2 -P 2 t Bu)(CO) 10 ] (type F), and [Fe 3 Cp*(μ 3 -κ 1 :κ 2 :κ 2 -P 2 t Bu)(CO) 8 ] (type G) …”

Coordination chemistry of hepta-tert-butylnonaphosphane

“…1–3 One class of cyclic P n frameworks is constituted by the cyclooligophosphanes cyclo -(P n R m ) ( n ≥ m ) which are isolobal to cycloalkanes. Although a relatively large number of cyclooligophosphanes has been described 2–5 and several metal carbonyl complexes are known, 6–26 there are only a few examples of coordination compounds with other co-ligands than carbonyl. 27–31 This fact is astonishing as compounds containing several phosphorus atoms with free lone pairs of electrons should be considered as ideal ligands in metal complexes due to the variety in coordination possibilities and the soft properties of phosphorus( iii ) according to the HSAB concept.…”