Synthesis and characterization of cyclopentadienylnickel(II) thiolates. Crystal structure of [(η⁵-C₅H₅)Ni(SC₆H₅) (PPh₃)]

The thiolate complexes CpNi(SR)(PPh₃) (1), (Cp = η⁵-C₅H₅, R =1cr; C₆H₅ and C₆H₄Me-4 were prepared by the reaction of CpNi(PPh₃) (X =1cr; Cl, Br, or I) with HSC₆H₅ and HSC₆H₄Me-4 respectively, in the presence of Et₃N. The structure of CpNi(SC₆H₅)(PPh₃) (1a) was determined by X-ray crystallography. The reaction of CpNiX(PPh₃) with the dithiols, toluene-dithiol and HS(CH₂)_xSH (x = 2, 3) resulted in the loss of PPh₃ and the formation of complexes of general formula CpNi(HS₂R′) (R′=1cr; C₆H₃Me-4) (2a) or R′ =1cr; (CH₂)_x where x = 2, 3 (2b and 2c). However, when butanedithiol was used in the same reaction the product was CpNi{S(CH₂)₄SH}(PPh₃) (1c).