Control of S-based aggregation: designed synthesis of NiM2 and Ni2M trinuclear complexes.
Modification of the nickel dithiolate metalloligand, Ni(bme-daco) [where bme-daco = bis(mercaptoethyl)diazacyclooctane] or Ni-1, by oxygenation of one thiolate into a sulfinate, Ni(mese-daco) [where mese-daco = (mercaptoethyl)(sulfinatoethyl)diazacyclooctane] or Ni-2, restricts the ligating ability to monodentate and is expected to reduce the donor ability of the remaining thiolate S. Nevertheless, the Ni-2 complex forms a stable thiolate S-bound adduct of W0(CO)5, (Ni-2)W(CO)5, a complex whose upsilon(CO) IR spectrum reports insignificant differences in the donor abilities of Ni-1 and Ni-2 in (eta1-NiN2S2)W(CO)5 complexes. In the presence of the strong sulfophile CuI, a CuNi2 trimetallic, (Ni-2)2CuBr, was isolated. Another trimetallic, (mu-eta2-Ni-1)[W(CO)5]2, demonstrated the Ni(bme-daco), Ni-1, unit to bridge low-valent metals in a transoid configuration, yielding W-W distances of over 5 A.
Jeffery
Stephen P
SP
Department of Chemistry, Texas A&M University, College Station, Texas 77843-3255, USA.
Singleton
Michael L
ML
Reibenspies
Joseph H
JH
Darensbourg
Marcetta Y
MY