Mp. Devery et al., THE COORDINATION AND REARRANGEMENT OF SOME ORGANIC CHALCOGENIDES ON ARHODIUM-RHODIUM BOND - THE REACTIONS WITH DIALKYLSULFANES AND ALKANETHIOLS, Journal of organometallic chemistry, 551(1-2), 1998, pp. 195-206
When solutions of [Cp2Rh2(mu-CO)(mu-eta(2):eta(2)-CF3C2CF3)] (I) in pe
troleum ether or chlorinated hydrocarbons were treated with the dialky
lsulfanes SRR'(R = R' = Me, Et, Pr, Bz; RR'= Meat), the addition produ
cts [Cp2Rh2(CO)(SRR')(mu-eta(1):eta(1)-CF3C2CF3)] (III, a-e) were form
ed reversibly. The complexes (III) have been characterized spectroscop
ically in solutions containing excess ligand. Removal of excess ligand
and solvent regenerated (I). When left in solution, a number of the d
ialkylsulfane complexes underwent interesting transformations. The com
plex (IIIa, R = R' = Me) converted to Cp2Rh2{mu-eta(1):eta(2)-C(CF3)C(
CF3)H}(mu(2)-SEt)] (IVa, R = Et); this involves a beta-proton transfer
accompanied by a Stevens rearrangement to convert (S(CH2-)CH3) to (SC
H2CH3)(-). The structure of (IVa) was determined by X-ray crystallogra
phy. Two rearrangement products were formed when (IIIb, R = R' = Et) w
as left in solution. One was characterized from spectroscopic data as
h2{mu-eta(1):eta(2)-C(CF3)C(CF3)H}(mu(2)-SCHMeEt)] (IVb), which is for
med by a Stevens rearrangement after transfer of a beta-proton. The ot
her was identified as (IVa, R = Pt), which is formed after proton abst
raction from a gamma-carbon followed by elimination of ethene. A numbe
r of mu-thiolato complexes (IVa-h, R = Me, Et, Pr, CHMeEt, Pr-i, Bu, B
u-t and Ph) were formed directly by treatment of (I) with the appropri
ate alkanethiol RSH. In some instances (R = CHMeEt, Pr-i, and Bu-t), a
second product of formula ){mu-eta(2):eta(1)-CH(CF3)C(CF3)(SCRRR3)-R-
1-R-2}] (VI, a-c) was formed. The molecular structure of (VI,, R-1 = H
, R-2 = R-3 = Me) was determined by single crystal X-ray diffraction a
nalysis. (C) 1998 Elsevier Science S.A.