A series of chemic
al
and electrochemic
al tr
ansform
ations of systems in which
a {Mo
2Cp
2(
![](/im<font color=)
ages/entities/mgr.gif">-SMe)
3} core is bridged by
a ![](/im<font color=)
ages/entities/mgr.gif">-C
2H
nR lig
and (
n = 0-4)
are described in this p
aper. There
action of the
alkylidene complex [Mo
2Cp
2(
![](/im<font color=)
ages/entities/mgr.gif">-SMe)
3(
![](/im<font color=)
ages/entities/mgr.gif">-
![](/im<font color=)
ages/gifch
ars/et
a.gif" BORDER=0 >
1:
![](/im<font color=)
ages/gifch
ars/et
a.gif" BORDER=0 >
2-CHCH
2Tol)](BF
4) (
1) with LiBu
nat 0
![](/im<font color=)
ages/entities/deg.gif">C produces the
![](/im<font color=)
ages/entities/mgr.gif">-
![](/im<font color=)
ages/gifch
ars/sigm
a.gif" BORDER=0 >,
![](/im<font color=)
ages/gifch
ars/pi.gif" BORDER=0 >-vinyl complex [Mo
2Cp
2(
![](/im<font color=)
ages/entities/mgr.gif">-SMe)
3((
![](/im<font color=)
ages/entities/mgr.gif">-
![](/im<font color=)
ages/gifch
ars/et
a.gif" BORDER=0 >
1:
![](/im<font color=)
ages/gifch
ars/et
a.gif" BORDER=0 >
2-CH=CHTol] (
2) in goodyield. The molecul
ar structure of
2 h
as been confirmed by X-r
ay
an
alysis. Upon tre
atmentwith N
aBH
4 1 is re
adily converted into the semibridging
alkyl species [Mo
2Cp
2(
![](/im<font color=)
ages/entities/mgr.gif">-SMe)
3(
![](/im<font color=)
ages/entities/mgr.gif">-CH
2CH
2Tol)] (
3), which is
also formed by electrochemic
al reduction of
1 in
acidic medium.NMR
and X-r
ay diffr
action studies of
3 are consistent with, but do not definitively est
ablish,the presence of
a ![](/im<font color=)
ages/gifch
ars/et
a.gif" BORDER=0 >
1 ![](/im<font color=)
ages/gifch
ars/
alph
a.gif" BORDER=0>-
agostic inter
action. Density function
al theory h
as been used to confirmthe presence of
agostic inter
actions in both
1 and
3 and
also to explore the exch
ange p
athw
aysfor these hydroc
arbyl dimolybdenum systems. Electrochemic
al tr
ansform
ation of the
![](/im<font color=)
ages/entities/mgr.gif">-
alkylidene complex
1 gives
3 as the m
ajor product when
acid is present
and
a mixture of
2 and
3 when
acid is
absent, production of
2 being f
avored by low initi
al concentr
ations of
1. Theoretic
al, spectroscopic,
and diffr
action d
at
a are used to expl
ain the form
ation
andstructures of closely rel
ated [Mo
2Cp
2(
![](/im<font color=)
ages/entities/mgr.gif">-SMe)
3(
![](/im<font color=)
ages/entities/mgr.gif">-C
2H
nR]
z+ complexes (
n = 0-4
and
z = 0, 1),including
1-
3.