Beiträge zur Komplexchemie der Phosphine und Phosphinoxide, XXVII. Übergangsmetall‐Aminoalkylphosphin‐Komplexe Teil 1: Nickelkomplexe

Abstract

Aminoalkylphosphine C6H6HPCH2 · CH2X (X = NH2), N(CH3)2, ; (C6H5)2PCH2 · CH2 · CH2X (X) = NH2, N = CHC6H5, NHC(S)NHC6H5) – reagieren unter geeigneten Bedingungen mit Nickelsalzen zu Koordinationsverbindungen des Typs NiX2 und NiX2()2. Im Falle der PH‐funktionellen ‐Liganden bilden sich unter Abspaltung von HX auch Phosphid‐amininnerkomplexe . Chelataktivität der ‐Liganden sowie Struktur und Eigenschaften der Koordinationsverbindungen werden diskutiert.

Preparation, Crystal Structures, and Spectroscopic and Redox Properties of Nickel(II) Complexes Containing Phosphane–(Amine or Quinoline)‐Type Hybrid Ligands and a Nickel(I) Complex Bearing 8‐(Diphenylphosphanyl)quinoline

“…[15] In contrast, complexes of the analogous P-Ntype ligand having an asymmetric phosphorus donor atom, namely (2-aminoethyl)methylphenylphosphane (MePhP-CH 2 CH 2 NH 2 : MePhPea), are limited to those of cobalt(III), [12c] palladium(II), and platinum(II). [16] Moreover, studies on the molecular structures and properties of metal complexes with 8-quinolylphosphanes are also scarce.…”

Preparation and characterization of mixed-ligand cobalt(iii) complexes containing (3-aminopropyl)dimethylphosphine (pdmp). Conformation of the six-membered pdmp chelate ring

“…In this study the synthesis of the corresponding edmp complexes, [Co(acac)(edmp) 2 ](PF 6 ) 2 (8), has also been attempted by a reaction of Li(acac) and either the dichloro complex of 2 or fac- [Co(edmp) 3 ]Cl 3 . 15 Both starting compounds gave almost the same results, affording only one product in ∼70% isolated yield.…”

“…The filtered solution was applied on a column (φ 3.5 × 50 cm) of Toyopearl HW-40 resin; two orange bands were resulted by elution with methanol. From the faster moving minor band, redorange crystals of trans(N,N)- [Co(acac) (8). A mixture of fac-[Co(edmp) 3 ]Cl 3 (0.30 g, 0.62 mmol) and Li(acac) (0.13 g, 1.2 mmol) in methanol (50 cm 3 ) was stirred at 30 • C overnight.…”

“…Aminoalkylphosphines are hemilabile didentate ligands, 1 and have recently attracted much interest in application of their transitionmetal complexes as effective homogeneous catalysts, 2,3 anticancer agents, 4,5 and others. [6][7][8][9][10] We have extensively studied various metal complexes bearing such aminoalkylphosphines, [11][12][13][14][15][16][17][18][19][20][21] and found that the ligands have a strong binding ability even toward the hard cobalt(III) ions. 12- 19 In particular, as the most fundamental and sterically least demanding amine-phosphine hybrid ligand, (2-aminoethyl)dimethylphosphine (H 2 NCH 2 CH 2 PMe 2 = edmp) has been used for preparation of a series of cobalt(III) complexes, fac- [Co(edmp) 3 ] 3+ , 12 trans(Cl,Cl)-cis(P,P)-[CoCl 2 (edmp) 2 ] + , 13,14 [Co(en) 3-n (edmp) n ] 3+ (en = ethane-1,2-diamine; n = 1 or 2) 15 and [Co(acac) 3-n (edmp) n ] n+ (acac = pentane-2,4-dionate), 16 and their crystal structures as well as their NMR, UV-vis absorption, and CD spectroscopic properties have been investigated.…”

Pyridylphosphines

“…Nand P-Derlvatlves Typical P-derivatives of pyridylphosphines include oxides,5'7'80-84 sulfides,2'5'7-83 selenides,7 methides,17'18'80 and methylphosphonium salts.2'5 '17,18 Pyridylphosphines were smoothly converted to the corresponding P-oxides with chloroamine-T5 or aqueous H2O2;5'80'84'86 '153 whereas, the use of m-chloroperbenzoic acid or peracetic acid can result in both Pand IV-oxidation.80,81 '86 The preparation of P-sulfides2'5 or P-selenides7,87 was readily accomplished by melting the corresponding phosphine with molecular sulfur or selenium, respectively. Bisphosphine 39 in the presence of neat excess Mel afforded the trismethiodide 40, which loses 1 equiv of Mel on standing at room temperature or heating (80 °C) for 3 h in vacuo giving the bis-P,P-methiodide 41.25 Slow aerial oxidation of 39 occurred upon standing for several weeks to generate the PP-dioxide (42), whereas with sulfur or selenium, it was converted stepwise to the mono-P-derivatives 43 and then bis-PP-deriva-tives25 44 (Scheme 14). 2-(pyr)3P ( 5) CDCls -0.05 76,84…”