Abstract

Abstract 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)3S4C4Ph4], 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)Å, β = 116.69(6)[ddot]. 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)Å, respectively. Complex 3 crystallizes in space group P21/n, with 4 molecules per unit cell, a=10.07(1), b=18.22(2) Å, c=15.36(2) Å, β = 94.56(8)[ddot], 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) Å, respectively. The coordination geometry of Ni is slightly tetrahedrally distorted from planar, with bond angles S-Ni-S of 87.6(1)[ddot], (CH2)S-Ni-S(CH2), 97.7(1)[ddot] and the mean of S-Ni-S(CH2) bond angles 162(2)[ddot]. The 1H NMR spectrum of 2 in CD2Cl2 shows the presence only of the one isomer and is temperature independent between—50[ddot] and + 50[ddot]C. The 1H NMR spectrum of 3 is temperature dependent due to dynamic equilibrium between the cis-anti- and cis-syn-isomers.

Talk to us

Join us for a 30 min session where you can share your feedback and ask us any queries you have

Schedule a call

Disclaimer: All third-party content on this website/platform is and will remain the property of their respective owners and is provided on "as is" basis without any warranties, express or implied. Use of third-party content does not indicate any affiliation, sponsorship with or endorsement by them. Any references to third-party content is to identify the corresponding services and shall be considered fair use under The CopyrightLaw.