SYNTHESIS, STRUCTURES AND DYNAMIC PROPERTIES OF TRIMETHYLENE-BIS(CIS-STILBENE-1,2-DITHIOLATO)NICKEL(II) AND TETRAMETHYLENE-BIS(CIS-STILBENE-1,2-DITHIOLATO)NICKEL(II)

The unusual, structurally dynamic behaviour of the Ni(II) dialkyldithiolene Ni[(CH3)2S4Ph4], 1, in solution prompted a study of the related macrocyclic complexes, Ni[(CH2)3S4CPh4], 2, and Ni[(CH2)4S4C4Ph4], 3, whose synthesis, structures and dynamic properties in solution are described. Complex 2, isolated as a CHCl3 inclusion compound, crystallizes in space group C2/c with 8 molecules per unit cell, a = 29.26(2), b = 8.170(4), c = 30.76(2) angstrom, beta = 116.69(6)-degrees. The complex has the cis-syn configuration with respect to the Ni-S(CH2)- bonds and the coordination geometry of Ni is essentially square planar, with mean Ni-S and Ni-S(CH2) bond lengths of 2.174(4) and 2.162(5) angstrom, respectively. Complex 3 crystallizes in space group P2(1)/n, with 4 molecules per unit cell. a = 10.07(1), b = 18.22(2) angstrom, c = 15.36(2) angstrom, beta = 94.56(8)-degrees, and the Ni S(CH2)- bonds are in the cis-anti-configuration. The mean Ni-S-and Ni-S(CH2) bond lengths are 2.156(5) and 2.153(9) angstrom, respectively. The coordination geometry of Ni is slightly tetrahedrally distorted from planar, with bond angles S-Ni-S of 87.6(1)-degrees, (CH2)S-Ni-S(CH2), 97.7(1)-degrees and the mean of S-Ni-S(CH2) bond angles 162(2)-degrees. The H-1 NMR spectrum of 2 in CD2Cl2 shows the presence only of the one isomer and is temperature independent between -50-degrees and +50-degrees-C. The H-1 NMR spectrum of 3 is temperature dependent due to dynamic equilibrium between the cis-anti- and cis-syn-isomers.