Reaction of Mo Mo doubly-bonded complexes (η5-RC5H4) 2Mo2 (CO) 2 (μ-SPh) 2 with elemental selenium. Synthesis and structural characterization of some novel sulfurselenium quadruply-bridged molybdenum complexes

Article abstract of DOI:10.1016/S0277-5387(98)00178-8

The reaction of Mo Mo doubly-bonded (η⁵-RC₅H₄) ₂Mo₂ (CO) ₂ (μ-SPh) ₂ (R = MeO₂C, EtO₂C) with elemental selenium in toluene at reflux results in formation of a series of sulfurselenium quadruply-bridged complexes transanti- (η⁵-RC₅H₄) ₂Mo₂ (μ-Se) ₂ (μ-SPh) ₂ (1a, R = MeO₂C ; 2a, R = EtO₂C) , transsyn- (η⁵-RC₅H₄) ₂Mo₂ (μ-Se) ₂ (μ-SPh) ₂ (1b, R = MeO₂C ; 2b, R = EtO₂C) , and cissyn- (η⁵-RC₅H₄) ₂Mo₂ (μ, η² : η²-Se₂) (μ-SPh) ₂ (1c, R = MeO₂C ; 2c, R = EtO₂C) in 58% and 53% overall yields, respectively. The structures of all these new products have been characterized by elemental analysis, IR, ¹H NMR and MS spectroscopies, as well as for 2c by X-ray crystallography.

Full text of DOI:10.1016/S0277-5387(98)00178-8

Polyhedron Vol[ 06\ No[ 10\ pp[ 2648Ð2653\ 0887
Þ 0887 Elsevier Science Ltd
Pergamon
All rights reserved[ Printed in Great Britain
9166Ð4276:87 ,08[99¦9[99
\
PII ] S9166Ð4276"87#99067Ð7
Reaction of Mo1Mo doubly!bonded complexes
"h4!RC4H3#1Mo1"CO#1"m!SPh#1 with elemental
selenium[ Synthesis and structural
characterization of some novel sulfur:selenium
quadruply!bridged molybdenum complexes
Li!Cheng Song\aꢀ Ji!Quan Wanga and Xiao!Ying Huangb
a Department of Chemistry\ Nankai University\ Tianjin 299960\ P[R[ China
b State Key Laboratory of Structural Chemistry\ Fuzhou 249991\ P[R[ China
"Received 17 January 0887 ^ accepted 13 April 0887#
Abstract*The reaction of Mo1Mo doubly!bonded "h4!RC4H3#1Mo1"CO#1"m!SPh#1 "R ꢁ MeO1C\ EtO1C#
with elemental selenium in toluene at re~ux results in formation of a series of sulfur:selenium quadruply!
bridged complexes trans:anti!"h4!RC4H3#1Mo1"m!Se#1"m!SPh#1 "0a\ R ꢁ MeO1C ^ 1a\ R ꢁ EtO1C#\ trans:syn!
"h4!RC4H3#1Mo1"m!Se#1"m!SPh#1 "0b\ R ꢁ MeO1C ^ 1b\ R ꢁ EtO1C#\ and cis:syn!"h4!RC4H3#1Mo1"m\ h1 ] h1!
Se1#"m!SPh#1 "0c\ R ꢁ MeO1C ^ 1c\ R ꢁ EtO1C# in 47) and 42) overall yields\ respectively[ The structures of
all these new products have been characterized by elemental analysis\ IR\ 0H NMR and MS spectroscopies\ as
well as for 1c by X!ray crystallography[ Þ 0887 Elsevier Science Ltd[ All rights reserved
Keywords] Mo1Mo double bond ^ selenium ^ reaction ^ crystal structure[
———————————————————————————————————————————————
Although group 5 metal triply!bonded complexes selenium
quadruply!bridged
dimolybdenum
"h4!RC4H3#1M1"CO#3 "M ꢁ Cr\ Mo\ W# have been complexes\ to the best of our knowledge\ are the _rst
extensively studied ð0\1Ł\ the corresponding metalÐ examples[
metal doubly!bonded complexes "h4!RC4H3#1M1
"CO#1"m!SR#1 are little explored so far ð2\3Ł[ On the
RESULTS AND DISCUSSION
basis of our recent work concerning this project ð4Ł
and in order to further develop the chemistry of the
group 5 metal doubly!bonded complexes\ we carried
out reaction of "h4!RC4H3#1Mo1"CO#1"m!SPh#1
"R ꢁ MeO1C\ EtO1C# ð5Ł with selenium powder in
re~uxing toluene[ Herein we report the detailed syn!
thetic procedures and structural characterization of
six novel dimolybdenum complexes prepared by the
above!mentioned reaction ] trans:anti!"h4!RC4H3#1
It was found that reaction of Mo1Mo doubly!
bonded complexes "h4!RC4H3#1Mo1"CO#1"m!SPh#1
"R ꢁ MeO1C\ EtO1C# ð5Ł\ as a mixture of trans:anti
and trans:syn isomers\ with excess selenium powder
in toluene at re~ux for 3 h resulted in complete dis!
appearance of the doubly!bonded starting material
and in the formation of several products\ as evidenced
by TLC analysis[ After solvent had been removed\ the
residue was subjected to TLC separation to give three
major bands[ The _rst blue band a}orded the com!
plexes trans:anti!"h4!RC4H3#1Mo1"m!Se#1"m!SPh#1 "0a\
R ꢁ MeO1C ^ 1a\ R ꢁ EtO1C#\ the second blue band
gave the complexes trans:syn!"h4!RC4H3#1Mo1"m!
Se#1"m!SPh#1 "0b\ R ꢁ MeO1C ^ 1b\ R ꢁ EtO1C#\ and
the third yellow band produced cis:syn!"h4!
RC4H3#1Mo1"m\ h1 ] h1!Se1#"m!SPh#1 "0c\ R ꢁ MeO1C ^
Mo1"m!Se#1"m!SPh#1\
trans:syn!"h4!RC4H3#1Mo1
"m!Se#1"m!SPh#1 and cis:syn!"h4!RC4H3#1Mo1"m\ h1 ]
h1!Se1#"m!SPh#1 "R ꢁ MeO1C\ EtO1C#[ Although
sulfur:sulfur and selenium:selenium quadruply!
bridged transition!metal dinuclear complexes have
appeared in the literature ð6Ł\ such mixed sulfur:
ꢀ Author to whom correspondence should be addressed[
2648

2659
L[!C[ Song et al[
1c\ EtO1C#\ as shown in Scheme 0[ Note that the one singlet at about 6 ppm for its phenyl groups and
terminologies of trans and cis for complexes 0aÐc and showed two broad singlets in the range of 4[13Ð4[41
1a*c refer to the relative positions of the two naked ppm for its substituted cyclopentadienyl rings\
Se atoms "or the two S atoms attached to phenyl whereas that of 1c showed one triplet at 0[19 ppm and
group# with respect to the Mo0Mo vector\ while one quartet at 3[07 ppm for its ethyl groups\ one
those of anti and syn refer to the mutual orientations singlet at 6[19 ppm for its phenyl groups and two
of the two phenyl groups with respect to their attached broad singlets in the range 4[39Ð4[61 ppm for its sub!
planar Mo1S1 ring for 0a\ b and 1a\ b\ and to their stituted cyclopentadienyl rings[ The IR spectra of 0aÐ
attached butter~y Mo1S1 skeleton for 0c and 1c[ All c and 1aÐc are quite similar[ Besides the bands for ester
these new complexes have been characterized by carbonyl\ their IR spectra all showed weak absorption
elemental analysis\ IR\ 0H NMR and MS spec! bands in the range of 199Ð449 cm−0 corresponding
0
troscopies[ The H NMR spectra of 0a and 0b dis! to the stretching vibrations of Mo0S and Mo0Se
played one singlet at ca 2[63 ppm for their methyl bonds[ In addition\ the mass spectra of 0a\ b and 1a\
groups\ whereas those of 1a and 1b exhibited one b demonstrated their respective molecular ion peaks
triplet at ca 0[14 ppm and one quartet at ca 3[14 ppm and corresponding fragment ion peaks\ which are in
for their ethyl groups[ In addition\ they all showed good agreement with their formulations[ According
three to four multiplets in the range of 5[13Ð6[39 ppm to the similar reaction of the Mo1Mo doubly bonded
for the phenyl groups and the substituted cyclo! complex Cp1Mo1"CO#1"m!SMe#1 with elemental sulfur
pentadienyl rings[ The 0H NMR spectrum of 0c ð7Ł\ the formation of 0a\ b and 1a\ b in this kind of
showed one singlet at 2[46 ppm for its methyl groups\ reaction is not unexpected ^ in addition\ some single
Scheme 0[

Reaction of Mo1Mo complexes with elemental selenium
2650
crystal structures of the compounds similar to 0a\ b MoC4H3CO1Et!h4 moiety is quadruply!bridged by a
and 1a\ b have been determined "see below for details#[ diselenido and two benzenethiolato ligands\ and the
However\ in this kind of reaction the formation of 0c two substituted cyclopentadienyl rings are perfectly
and 1c is unexpected[ So\ in order to unambiguously eclipsed[
con_rm their structures\ an X!ray di}raction analysis
The bond distance of Se"0#0Se"1# ð1[208"0# _Ł in
for 1c was undertaken[ Figures 0 and 1 represent its 1c is close to that in "m!Se1#Fe1"CO#5 ð1[182"1# _Ł ð8Ł
single crystal molecular structure and its molecular and slightly shorter than the normal Se0Se single
projection\ respectively[ Table 0 shows its selected bond distances of 1[22"0# to 1[27"0# _ ð09Ł[ The four
bond distances and angles[
bridged atoms in 1c form a plane\ which is parallel to
As seen from Figs 0 and 1 the h4!Et1OCC4H3Mo! the two substituted cyclopentadienyl ring planes and
Fig[ 0[ ORTEP view of 1c\ drawn with 29) probability ellipsoids[
Fig[ 1[ The molecular projection of 1c along its Mo0Mo bond[

2651
L[!C[ Song et al[
Table 0[ Selected bond distances "_# and angles "># for 1c
Mo"0#0Mo"1#
Mo"0#0Se"0#
Mo"0#0Se"1#
Mo"1#0Se"0#
Mo"1#0Se"1#
1[550"0#
1[458"0#
1[461"0#
1[457"0#
1[447"0#
Se"0#0Se"1#
Mo"0#0S"0#
Mo"0#0S"1#
Mo"1#0S"0#
Mo"1#0S"1#
1[208"0#
1[308"1#
1[326"1#
1[325"1#
1[311"1#
S"0#0Mo"0#0Mo"1#
S"1#0Mo"0#0Se"0#
S"1#0Mo"0#0Se"1#
S"1#0Mo"0#0Mo"1#
Se"0#0Mo"0#0Se"1#
Se"0#0Mo"0#0Mo"1#
Se"1#0Mo"0#0Mo"1#
Mo"1#0Se"0#0Mo"0#
Se"0#0Se"1#0Mo"1#
Se"0#0Se"1#0Mo"0#
46[96"3#
S"1#0Mo"1#0Mo"0#
S"0#0Mo"1#0Mo"0#
Se"1#0Mo"1#0Se"0#
Se"1#0Mo"1#0Mo"0#
Se"0#0Mo"1#0Mo"0#
Se"1#0Se"0#0Mo"1#
Se"1#0Se"0#0Mo"0#
Mo"1#0Se"1#0Mo"0#
Mo"0#0S"0#0Mo"1#
Mo"1#0S"1#0Mo"0#
46[95"3#
45[35"4#
42[67"2#
48[91"2#
47[70"2#
51[78"2#
51[17"2#
51[37"2#
55[36"4#
55[30"4#
003[29"4#
72[22"4#
45[42"3#
42[51"2#
47[68"2#
47[49"2#
51[39"2#
52[22"2#
52[09"2#
bisects the Mo0Mo vector perpendicularly[ The non! Mo1"CO#1"m!SPh#1 "R ꢁ MeO1C\ EtO1C# were pre!
bonding distances between the bridged atoms are pared according to published method ð5Ł[ IR spectra
1[728"1#\ 2[213"6# and 2[221"1# _ in 1c[ These dis! were recorded on NICOLET MAGNA FT!649 and
0
tances fall in the range of the sum of van der Waals BIO!RAD FTS!39 infrared spectrophotometers[ H
radii of corresponding S:S\ S:Se atoms\ and indicate NMR spectra were recorded on a JEOL FX 89Q
a weak interaction between the bridging atoms[ Com! NMR spectrometer[ C:H analyses and MS deter!
plexes 0a\ b and 1a\ b are d1Ðd1 dimers and would minations were performed by a 139C analyzer and an
have a s1d1 electronic con_guration ð00Ł[ This suggests HP 4877A spectrometer\ respectively[ Melting points
a double bond present between two Mo"¦IV# atoms\ were determined on a YANACO MP!499 micro!
which is consistent with the 07!e rule[ However\ 0c melting point apparatus[
and 1c are d2Ðd2 dimers with a s1d1dꢀ1 electronic con!
_guration ð00Ł\ which would suggest a single bond
between two Mo"¦III# atoms[ The single Mo0Mo
bond assignment for 0c and 1c is also in good agree!
ment with the 07!e rule[ It is worth noting that the
Mo0Mo bond length of 1[550"0# _ in 1c is quite
short for a normal single bond due to the e}ect of the
four bridging ligands and the oxidation states of two
Mo"III# atoms ð01Ł[ Some other quadruply!bridged
dimolybdenum complexes in which the single
Mo0Mo bond length are very close to the Mo0Mo
double bond lengths are Cp1Mo1"m!SMe#3 ð1[592"1#
Preparation of 0a\ 0b and 0c
A 099 cm2 two!necked ~ask _tted with a magnetic
stir!bar\ a rubber septum\ and a re~ux condenser
topped with a nitrogen inlet tube was charged with
9[399
g
"9[451 mmol# of "h4!MeO1CC4H3#1
Mo1"CO#1"m!SPh#1\ 9[067 g "1[143 mmol# of selenium
powder and 29 cm2 of toluene[ The mixt[ was re~uxed
for 3 h[ Solvent was removed at red[ pres[ and the
residue was subjected to preparative TLC separation
using CH1Cl1 as eluent to give three major bands
"Blue\ sky!blue and yellow#\ from which were
obtained 9[019 g "15)# of 0a\ 9[969 g "04)# of 0b
and 9[979 g "06)# of 0c\ respectively[ 0a ] m[p[ 132Ð
133>C[ Found ] C\ 27[44 ^ H\ 1[60[ Calc[ for
C15H13Mo1O3S1Se1 ] C\ 27[23 ^ H\ 1[86)[ IR "KBr\
disk# ] 0608 vs "nCꢁO#\ 491 w\ 375 w\ 352 w\ 322 w\ 315
_Ł ð00Ł and CpꢀMo1Br3 "Cpꢀ ꢁ h4!0!"1\4!dimethoxy!
1
phenyl#!1\2\3\4!tetraphenylcyclo!pentadienylŁ ð1[580
"3# _Ł ð02Ł[ The other quadruply!bridged dimol!
ybdenum complexes with Mo1Mo double bond are
trans:anti!"h4!MeC4H3#1Mo1"m!S#1"m!SMe#1 ð1[471"0#
_Ł ð03Ł\ trans:anti!"h4!Me4C4#1Mo1"m!S#1"m!SMe#1
ð1[462"0# _Ł ð04Ł\ trans:syn!"h4!iPrC4H3#1Mo1"m!S#1"m!
StBu#1 ð1[476"0# _Ł ð05Ł and trans:syn!"h4!
C4H4#1Mo1"m!Se#1"m!SePh#1 ð1[542"1# _Ł ð06Ł[
0
w cm−0[ H NMR "CDCl2# ] d 2[61 "s\ 5H\ 1CH2#\
5[13Ð6[17 ðm\ 07H\ 1 "C5H4¦C4H3#Ł ppm[ MS "EI#\
m:z "rel[ int[# ] 719 "M¦\ 3[4)#\ 632 ð"M−PhŁ¦\ 5[7Ł\
691 ð"M−1MeO1C#¦\ 5[6Ł\ 514 ð"M−1Me!
O1C−Ph#¦\ 3[5Ł\ 463 ð"M−1C4H3CO1Me#¦\ 3[7Ł\ 405
EXPERIMENTAL
All reactions were carried out under prepuri_ed ð"C4H3#1Mo1SSe¦1 \ 2[2Ł\ 386 "PhMo1S1Se1¦\ 00[1#\
nitrogen using vacuum!line techniques[ Toluene was 373 "C4H3Mo1S1Se¦1 \ 6[7#\ 357 ð"C4H3#1Mo1S1Se¦\
distilled from sodium!benzophenone ketyl[ Pre! 7[1Ł\ 325 ð"C4H3#1Mo1SSe¦\ 4[1Ł\ 319 "Mo1S1Se1¦\
parative TLC was carried out on glass plates "15×08 00[6#\ 277 "Mo1SSe¦1 \ 7[7#\ 245 "Mo1Se1¦\ 2[4#\ 239
cm# coated with silica gel G "09Ð39 mm#[ "h4!RC4H3#1 "Mo1S1Se¦\ 5[8#\ 213 ð"C4H3#1Mo¦1 \ 2[5Ł\ 297

Reaction of Mo1Mo complexes with elemental selenium
2652
"Mo1SSe¦\ 4[6#\ 159 "Mo1S¦1 \ 2[6#\ 098 "PhS¦\ 05[7#\ "CDCl2# ] d 0[19 "t\ 5H\ J ꢁ 6[1 Hz\ 1CH2#\ 3[07 "q\
81 ðC4H3"CO#¦\ 34[0Ł\ 66 "Ph¦\ 26[4#[ 0b ] m[p[ 077>C 3H\ J ꢁ 6[1 Hz\ 1CH1#\ 4[39 ðbr s\ 3H\ 1"H2\ H3#Ł\
"dec[#[ Found ] 27[21 ^ H\ 1[81[ Calc[ for 4[61 ðbr s\ 3H\ 1"H1\ H4#Ł\ 6[19 "s\ 09H\ 1C5H4# ppm[
C15H13Mo1O3S1Se1 ] C\ 27[23 ^ H\ 1[86)[ IR "KBr\ MS "EI#\ m:z "rel[ int[# ] 548 ð"M−PhSSe#¦\ 9[5)Ł\
0
disk# ] 0619 vs "nCꢁO#\ 499 w\ 356 w cm−0[ H NMR 369 ð"EtO1CC4H3#1Mo1¦\ 9[8Ł\ 325 ð"C4H3#1
"CDCl2# ] d 2[66 "s\ 5H\ 1CH2#\ 5[49Ð6[99 ðm\ 07H\ 1 Mo1SSe¦\ 9[4Ł\ 393 ð"C4H3#1Mo1Se¦\ 9[4Ł\ 277
"C5H4¦C4H3#Ł ppm[ MS "EI#\ m:z "rel[ int[# ] 719 "Mo1SSe¦1 \ 9[7#\ 245 "Mo1Se1¦\ 9[4#\ 213 ð"C4H3#1
"M¦\
1[9)#\
639
ð"M−Se#¦\
1[8Ł\
691 Mo¦1 \ 9[3Ł\ 297 "Mo1SSe¦\ 1[9#\ 159 "Mo1S¦1 \ 0[9#\
ð"M−1MeO1CŁ¦\ 1[9Ł\ 514 ð"M−1MeO1C−Ph#¦\ 085 "Mo1¦\ 0[3#\ 098 "PhS¦\ 099#\ 87 "Mo¦\ 1[6#\ 81
2[4Ł\ 386 "PhMo1S1Se1¦\ 1[8#\ 373 "C4H3Mo1S1Se1¦\ ðC4H3"CO#¦\ 10[5Ł\ 66 "Ph¦\ 35[5#[
1[9#\ 277 "Mo1SSe1¦\ 1[2#\ 245 "Mo1Se1¦\ 0[4#\ 239
"Mo1S1Se¦\ 0[4#\ 213 ð"C4H3#1Mo1¦\ 0[8Ł\ 297
Structure determination of 1c
"Mo1SSe¦\ 0[1#\ 085 "Mo¦1 \ 6[2#\ 098 "PhS¦\ 23[3#\ 81
ðC4H3"CO#¦\ 21[8Ł\ 66 "Ph¦\ 099#[ 0c ] m[p[ 106Ð
Suitable single crystals of 1c for X!ray di}raction
107>C[ Found ] C\ 27[03 ^ H\ 2[12[ Calc[ for
study were obtained by slow evaporation of a
C15H13Mo1O3S1Se1 ] C\ 27[23 ^ H\ 1[86)[ IR "CsI\
CH1Cl1:hexane solution[ A single crystal with dimen!
disk# ] 0699 vs "nCꢁO#\ 497 w\ 377 w\ 323 w\ 258 w\ 226
sions of 9[39×9[29×9[14 mm for 1c was mounted on
w\ 169 w\ 146 w\ 118 w\ 197 w cm−0 0H NMR
[
a glass _bre with epoxy resin[ Data collections were
performed on a Enraf!Nonius CAD3 di}ractometer
equipped with a graphite monochromator at room
temperature "1220>C#[ Details of its crystal
parameters\ data collections and structure re_nements
are summarized in Table 1[ Lorentz and polarization
corrections\ and absorption correction were applied
to the data[ The structure was solved by the direct
"CDCl2# ] d 2[46 "s\ 5H\ 1CH2#\ 4[13 ðbr s\ 3H\ 1 "H2\
H3#Ł\ 4[41 ðbr s\ 3H\ 1 "H1\ H4#Ł\ 6[99 "s\ 09H\ 1C5H4#
ppm[
Preparation of 1a\ 1b and 1c
The similar reaction of 9[399 g "9[439 mmol# of "h4!
EtO1CC4H3#1Mo1"CO#1"m!SPh#1\ 9[060
g
"1[055
mmol# of selenium powder a}orded 9[975 g "08)# of
1a\ 9[908 g "3)# of 1b and 9[024 g "29)# of 1c\ 1a ]
m[p[ 126Ð127>C[ Found ] C\ 28[85 ^ H\ 2[17[ Calc[ for Table 1[ Details of crystal parameters\ data collections and
structure re_nements for 1c
C17H17Mo1O3S1Se1 ] C\ 28[81 ^ H\ 2[24)[ IR "CsI\
disk# ] 0699 vs "nCꢁO#\ 405 w\ 380 w\ 369 w\ 321 w\ 396
0
w\ 274 w\ 138 w cm−0[ H NMR "CDCl2# ] d 0[19 "t\
Molecular formula C17H17Mo1O3S1Se1
Molecular weight
Color and habit
Crystal system
Space group
a "_#
731[34
5H\ J ꢁ 6[1 Hz\ 1CH2#\ 3[13 "q\ 3H\ J ꢁ 6[1 Hz\
1CH1#\ 5[13Ð6[39 ðm\ 07H\ 1"C5H4¦C4H3#Ł ppm[ MS
"EI#\ m:z "rel[ int[# ] 423 ð"M−1Ph−1Se#¦\ 9[7)Ł\
373 "C4H3Mo1S1Se¦1 \ 0[3#\ 325 ð"C4H3#1Mo1SSe¦\
0[6Ł\ 319 "Mo1S1Se1¦\ 1[0#\ 277 "Mo1SSe1¦ 0[4#\ 245
"Mo1Se¦1 \ 1[9#\ 239 "Mo1S1Se¦\ 0[9#\ 297 "Mo1SSe¦\
yellow needle
monoclinic
P10:n "No[ 03#
00[415"2#
03[765"1#
06[946"3#
89[99
b "_#
c "_#
0[0#\ 098 "PhS¦\ 49[8#\ 81 ðC4H3"CO#¦\ 24[6Ł\ 66 "Ph¦\ a ">#
b ">#
85[03"1#
89[99
1897"0#
3
0[81
0537
47[5#[ 1b ] m[p[ 044Ð045>C[ Found ] C\ 28[78 ^ H\ 2[30[
Calc[ for C17H17Mo1O3S1Se1 ] C\ 28[81 ^ H\ 2[24)[ IR
"CsI\ disk# ] 0696 vs "nCꢁO#\ 493 w\ 389 w\ 350 w\ 279
w\ 223 w\ 134 w\ 120 w\ 105 w\ 197 w cm−0[ 0H NMR
"CDCl2# ] d 0[16 "t\ 5H\ J ꢁ 6[1 Hz\ 1CH2#\ 3[29 "q\
3H\ J ꢁ 6[1 Hz\ 1CH1#\ 5[43Ð6[97 Łm\ 07H\
1"C5H4¦C4H3#Ł ppm[ MS "EI#\ m:z "rel[ int[# ] 737
g ">#
V "_2#
Z
Dcalc "g cm−2
F"999#
#
m "cm−0
#
23[81
l"MoÐKa# "_#
Scan type
Scan width ">#
9[60958
v:1u scan
9[39¦9[24 tgu
³4[38
38[8
4507
4305
3061 "I − 2s"I##
232
9[943
9[956
"M¦\
1[9)#\
660
ð"M−Ph#¦\
2[3Ł\
503
ð"M−1Ph−Se#¦\ 3[1Ł\ 423 ð"M−1Ph−1Se#¦\ 1[6Ł\
405 ð"C4H3#1Mo1SSe1¦\ 1[4Ł\ 373 "C4H3Mo1S1Se¦1 \ Scan speed "> cm−0
#
3[7#\
357
ð"C4H3#1Mo1S1Se¦\
3[4Ł\
325
1umax ">#
No[ of re~ections measured
No[ of re~ections\ unique
No[ of re~ections observed\ n
No[ of variables\ p
R
Rw
GOF
ð"C4H3#1Mo1SSe¦\ 4[2Ł\ 319 "Mo1S1Se1¦\ 5[4#\ 277
"Mo1SSe¦1 \ 3[4#\ 245 "Mo1Se1¦\ 4[6#\ 239 "Mo1S1Se¦\
2[9#\ 213 ð"C4H3#1Mo1¦\ 0[5Ł\ 297 "Mo1SSe¦\ 1[1#\ 159
"Mo1S¦1 \ 0[0#\ 085 "Mo¦1 \ 1[9#\ 098 "PhS¦\ 49[1#\ 81
ðC4H3"CO#¦\ 39[0Ł\ 66 "Ph¦\ 46[0#[ 1c ] m[p[ 089Ð
080>C[ Found ] C\ 39[16 ^ H\ 2[12[ Calc[ for
C17H17Mo1O3S1Se1 ] C\ 28[81 ^ H\ 2[24)[ IR "CsI\
disk# ] 0696 vs "nCꢁO#\ 410 w\ 389 w\ 325 w\ 318 w\ 258
0[82
9[91
−0[67:¦0[72
Largest D:s in _nal cycle
Dr "min:max# "e _−2
#
w\ 243 w\ 218 w\ 117 w\ 192 w cm−0 0H NMR
[

2653
L[!C[ Song et al[
5[ Song\ L[!C[\ Wang\ J[!Q[\ Hu\ Q[!M[ and Huang\
X[!Y[\ Polyhedron\ 0886\ 05\ 1138[
6[ "a# Wachter\ J[\ J[ Coord[ Chem[\ 0876\ 04\ 108 ^
"b# Wachter\ J[\ An`ew[ Chem[ Int[ Ed[ En`l[\
0878\ 17\ 0502 ^ "c# Shibahara\ T[\ Coord[ Chem[
Rev[\ 0881\ 012\ 62[
methods "MITHRIL#[ The _nal re_nements were
accomplished by the full!matrix least!squares method
with anisotropic thermal parameters for non!hydro!
gen atoms[ All calculations were performed on Micro
VAX II computer using the TEXSAN program pack!
age[
7[ Li\ P[ and Curtis\ M[ D[\ Inor`[ Chem[\ 0889\ 18\
0131[
8[ Campana\ C[ F[\ Yip!Kwailo\ F[ and Dahl\ L[ F[\
Inor`[ Chem[\ 0868\ 07\ 2959[
09[ Zingaro\ R[ A[ and Copper\ W[ C[\ Selenium\ Van
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00[ Connelly\ N[ G[ and Dahl\ L[ F[\ J[ Am[ Chem[
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Acknowled`ements*We are grateful to the National Natural
Science Foundation of China\ the State Key Laboratory of
Structural Chemistry and the Special Foundation of State
Education Committee of China for _nancial support of this
work[
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