THE USE OF CHLOROALKYLDICHLOROARSINES IN HIBRID LIGAND SYNTHESIS. THE PREPARATION OF BUT-3-ENYLBIS(3-DIMETHYLARSINOPROPYL)ARSINE AND 3-DIMETHYLARSINOPROPYLBIS(BUT-3-ENYL)ARSINE, AND THEIR REACTION WITH NICKEL(II) SALTS TO FORM PENTACOORDINATE COMPLEXES. NOVEL NICKEL(II)-OLEFIN BONDS

Article abstract of DOI:10.1016/0022-328X(85)80069-3

Routes have been developed to the hitherto unobtainable arsine-olefin ligands (CH2=CHCH2CH2)_nAs(CH2CH2CH2AsMe2)_3-n (n= 1, tasol, but-3-enylbis(3-dimethylarsinopropyl)arsine; n= 2, dasdol, 3-dimethylarsinopropylbis(but-3-enyl)arsine) by making use of the difference in reactivity between the Cl-C and As-Cl bonds in the precursor Cl(CH2)_mAsCl2 (m = 2,3) molecules.Thus, the triarsine obtained by reaction of 2-chloroethyldichloroarsine with the Grignard reagent of 3-chloropropyldimethylarsine yields 2-chloroethylbis(3-dimethylarsinopropyl)arsine, from wich tasol is obtainable by subsequent reaction with either the Grignard reagent of vinyl bromide or, preferably, with vinyllithium.Similarly, 3-chloropropyldichloroarsine reacts with the Grinard reagent of 4-chlorobut-1-ene to form 3-chloropropylbis(but-3-enyl)arsine which, on reaction with sodium dimethyarsenide yields dasdol.The tasol ligand reacts with nickel(II) salts to form ⁺ (X = Cl, Br) and , the former are trigonal bipyramidal and contain a nickel(II)-olefin bond, and the latter are square pyramidal containing a coordination sphere.In addition, tasol forms a number of polynuclear complexes with nickel(II).The dasdol ligand acts as a bidentate arsine form only ⁺.The formation of novel nickel(II)-olefin bonds in the ⁺ cation is discussed.