Inorganica Chimica Acta p. 63 - 69 (1977)
Update date:2022-08-05
Topics:
Levason
McAuliffe
Murray
Thirtyfour complexes of 1,2-bis(methylphenylarisino)ethane (dase) and 1,3-bis(methylphenylarsino)propane (dasp) have been characterised. Interesting differences are observed in the complexing properties of these chelates. Thus, with cobalt(II) halides [Co(dase)2][CoX4], which contain planar cations, and pseudotetrahedral [Co(dasp)X2] are obtained. Nickel (II) halides form planar [NiLX2] complexes with dase, but with dasp form [Ni(dasp)X2]n (X = Cl, Br) which are pseudooctahedral in the solid state and planar in solution, and the pseudotetrahedral [Ni(dasp)I2]. The [Ni(dasp)2X] ClO4 are trigonal bipyramidal in the solid state (X = Cl, Br, I, NCS), but in solution [Ni(dasp)2(NCS)]+ appears to be square pyramidal, whilst the [Ni(dase)2X] ClO4 are square pyramidal in both the solid state and solution. The planar [Ni(dasp)(NCS)2] complex differs from the analogous dase species by losing ligand on recrystallisation to form the dimeric Ni2(dasp)3(NCS)4moiety. Planar [PdLX2] (L = dase, dasp, X = Cl, Br, I) species are formed, but no [PdL2X]+ complexescould be isolated. In the solid state [PdL(NCS)(SCN)] complexes are formed, and the dase species isomerises to [Pd(dase)(SCN)2] in dichloromethane. An attempt is made to relate the structural differences in the complexes to the chain length of the chelates.
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(1977)