107783-62-0Relevant articles and documents
A convenient synthetic protocol to 1,2-bis(dialkylphosphino)-ethanes
Doyle, Laurence R.,Heath, Alex,Low, Choon Heng,Ashley, Andrew E.
, p. 603 - 608 (2014)
1,2-Bis(dialkylphosphino)ethanes are readily prepared from the parent phosphine oxides, via a novel sodium aluminium hydride/sodium hydride reduction protocol of intermediate chlorophosphonium chlorides. This approach is amenable to multi-gram syntheses, utilises readily available and inexpensive reagents, and benefits from a facile non-aqueous work-up in the final reductive step.
Bis(di-tert-butylphosphino)ethane-nickel(0) Complexes
Poerschke, Klaus-Richard,Pluta, Christian,Proft, Bernd,Lutz, Frank,Krueger, Carl
, p. 608 - 626 (2007/10/02)
Ni(cdt) reacts with tBu2PC2H4PtBu2 in pentane at 20 deg C to yield brownish crystals of (tBu2PC2H4PtBu2)Ni(η2-C12H18) (1).The molecular structure of 1, as established by X-ray crystallography, exhibits a trigonal-planar coordination geometry of the nickel center with a η2-bonded cdt ligand.In the crystal 1 exists as two enantiomers, which are determined by the left- or right-handed screw axis of the cdt ligand.The cdt ligand in 1 resists most typical displacement reactions but 1 reacts with CO at -78 deg C to afford the colorless 18e complex (tBu2PC2H4PtBu2)Ni(CO)2 (2).From the reaction of Ni(cod)2 with tBu2PC2H4PtBu2 yellow needles of (tBu2PC2H4PtBu2)Ni(η2-cod) (3) are obtained.Low temperature NMR spectroscopy established that only one diene C=C bond is coordinated to nickel(0).At higher temperatures a rapid exchange of the coordinated and unbound C=C bonds is induced.When solutions of 3 are kept at 20 deg C for several days the dinuclear, almost insoluble yellow complex tBu2PC2H4PtBu2)Ni>2(μ-η2,η2-cod) (4) precipitates.The reaction of Ni(C2H4)3 and tBu2PC2H4PtBu2 affords orange (tBu2PC2H4PtBu2)Ni(C2H4) (5).From Ni(1,5-hexadiene)2 and tBu2PC2H4PtBu2 in 1,5-hexadiene the yellow-greenish complex (tBu2PC2H4PtBu2)Ni(η2-C6H10) (6) is obtained.As for 3, only one diene C=C bond is coordinated to nickel(0), but the structure is fluxional with exchange of the coordinated and unbound C=C bonds (NMR at 20 degC).From a solution of 6 in pentane the dinuclear, diastereomeric compounds rac/meso-tBu2PC2H4PtBu2)Ni>2(μ-η2,η2-C6H10) (7a,b) separate in large yellow crystals.In similar reactions the 1,6-heptadiene complexes (tBu2PC2H4PtBu2)Ni(η2-C7H12) (8) and rac/meso-tBu2PC2H4PtBu2)Ni>2(μ-η2,η2-C7H12) (9a,b) are also obtained.In 6, 7a,b, 8, and 9a,b the open-chain diene ligands can easily be displaced, e.g., by ethene to afford 5.Thus, complexes 6, 7a,b, 8, 9a,b are the most reactive.These complexes react readily (the ethene derivative 5 also reacts but very slowly) with butadiene to yield large yellow cubes of (tBu2PC2H4PtBu2)Ni(η2-C4H6) (10), which is also fluxional.The alkene complexes 5, 6, 7a,b, 8, 9a,b, 10 react with ethyne to yield yellow-brownish crystalline (tBu2PC2H4PtBu2)Ni(C2H2) (11).Key Words: Alkenens, Ethyne, Nickel(0), Phosphane, X-Ray