An electrochemical study of M(dtc), complexes, M = Pd, Pt, established that these complexes can be reduced to the unstable M(dtch species and irreversibly oxidized to the tris complexes, M(dtc)i. although in low yields. A detailed study of the redox behaviour of the platinum tris compound, Pt(dtc)i, revealed that a two electron transfer process occurred, with a very rapid decomposition of the reduced species, according to
Pt(dtc); + Pt(dtc);+ Pt(dtclz + dtc-The electrochemical behaviour of the diseleno complexes, M(dsc)l and electrochemically generated M(dsc)i, M = Ni, Pd, Pt, closely parallels that of their dtc congeners.
'anod.
Pr -1.60 68 -1.59 143 -1.64 108 1.1 Et -1.50 88 -1.48 155 -1.56 131 1.5 nBu -1.50 68 -1.50 133 -1.56 114 1.3 Ph -1.44 58 -1.44 118 -1.47 72 1 A Bz -1.39 56 -1.37 113 -1.40 76 1.2 Pt(R2dtc)2 Et -2.09 Bu -2.08 -2.13 i-Pr -2.12 'In acetone vs. a Ag/AgCl (0.1 M LiCl-acetone) reference electrode. %idth at half peak height. 'Cathodic to anodic peak potential separation.
TABLE IV. Electrochemical Reduction of Metal Dise1enocarbamates.a J. G. h4. van der Linden and A. H. Dir Complexes Normal Pulse Polarography AC Voltammetry Cyclic Voltammetry Ecf E3/4 -El14 EP W/2 b cat. EP c .cat. WV) (VI (mV) C-W $f) $iix-Ni(Etzdsc)z -1.34 55 -1.36 123 -1.43 148 1.3 Ni(Bu2dsc)2 -1.38 71 -1.36 123 -1.42 105 1.2 Pdf&ds& -1.54 55 -1.53d 98 -1.59 111 1.9 Pd(Bu2dsc)2 -1.56 55 -1.54d 122 -1.60 101 1.4 pt(Et2w2 -1.87 -1.90 Pt(Bu2dsc)2 -2.10 -2.04 ?n acetone vs. Ag/AgCl electrode. %dth at half peak height. 'Cathodic to anodic peak potential separation. dAC frequency 35 Hz.