067
A[ Lehtonen\ R[ Sillanpaa : Polyhedron 07 "0888# 064Ð068
à Ã
form complexes having the formula ðW"eg#1"OC5H2R1?!
1\5#1Ł[
020>C ð7Ł#[ NMR "solvent CDCl2\ standard SiMe3#] dH
6[94 "m\ 1H#\ 5[70 "m\ 1H#\ 1[16 "d\ Jꢁ4 Hz\ 2H#[
According to X!ray studies\ two phenoxide ligands in
the mixed complexes are in cis!positions[
3[3[ Preparation of ðW"eg#1"OC5H2Me1!1\5#1Ł "3#
9[25 g "0[9 mmol# ðW"eg#2Ł and 9[25 g "1[1 mmol# 1\5!
Me1PhOAc were dissolved in 49 ml of chlorobenzene and
the reaction mixture was stirred under re~ux for six
hours[ The yellow solution was _ltered and the solvent
was evaporated yielding yellow microcrystals[ Crystals
for X!ray analysis were grown from ether by slow evap!
oration "304 mg\ 57)#[ The crystals decompose at tem!
peratures over 199>C in air[ NMR "solvent CDCl2\
standard SiMe3#] dH 6[02 "d\ Jꢁ7 Hz\ 1H#\ 5[85 "t\
Jꢁ7 Hz\ 0H#\ 4[32 "m\ 0H#\ 4[18 "m\ 1H#\ 4[06 "m\ 0H#\
0[06 "q\ 5H#[
3[ Experimental
Chemicals were from commercial origins and were
used without subsequent puri_cation[ ðW"eg#2Ł was pre!
pared as described earlier ð03Ł[ Substituted phenyl acet!
ates were prepared from phenols and acetic anhydride[
0H NMR spectra were recorded on a JEOL GSX!399
spectrometer[ The products are pure according to NMR
measurements[ The C and H elemental analyses failed
due to incomplete decomposition of the compounds dur!
ing the analysis[
i
3[4[ Preparation of ðW"eg#1"OC5H2 Pr1!1\5#1Ł "4#
3[0[ Preparation of ðW"OC5H4#5Ł "0#
ðW"eg#2Ł "9[43 g\ 0[4 mmol# and 1\5!iPr1PhOAc "9[69 g\
2[1 mmol# were dissolved in 49 ml of chlorobenzene and
the reaction mixture was allowed to re~ux for four hours[
The yellow solution was _ltered and evaporated to
dryness[ The oily residue was washed twice with 4 ml
of cold heptane and the remaining yellow powder was
extracted with ether "29 ml#[ Yellow crystals precipitated
from ether solution at −07>C "439 mg\ 44)# and decom!
pose over 199>C[ Crystals for X!ray analysis were grown
from hot heptane[ NMR "solvent CDCl2\ standard
SiMe3#] dH 6[00 "d\ Jꢁ7 Hz\ 1H#\ 5[83 "t\ Jꢁ6 Hz\ 0H#\
4[32 "m\ 0H#\ 4[16 "m\ 1H#\ 4[04 "m\ 0H#\ 2[50 "m\ 1H#\
0[06 "q\ 01H#[
ðW"eg#2Ł "9[61 g\ 1[9 mmol# and PhOAc "0[5 g\
01[4 mmol# were dissolved in 49 ml of chlorobenzene and
the mixture was allowed to re~ux for six hours[ During
this period the color of the solution turned intense red[
The solution was _ltered and the _ltrate was washed twice
with 09) aqueous NaOH "14 ml# and twice with water
"14 ml#[ Volatiles were evaporated in vacuum and the red
residue was dissolved in acetonitrile[ Slow evaporation of
solvent led to crystallization of ðW"OPh#5Ł as red needles
"619 mg\ 37)#[ m[p[ 86>C "lit[ 84Ð85>C ð7Ł#[ NMR "sol!
vent CDCl2\ standard SiMe3#] dH 6[02 "m\ 1H#\ 5[68 "m\
2H#[
3[1[ Preparation of ðW"OC5H3Cl!3#5Ł "1#
3[4[0[ X!ray crystal determinations
3!ClPhOAc "0[0 g\ 5[4 mmol# was added to the solution
of ðW"eg#2Ł "9[25 g\ 0[9 mmol# in chlorobenzene "49 ml#[
The reaction mixture was stirred under re~ux for eight
hours[ Washing of the _ltered solution with 09) aqueous
NaOH "14 ml# and water "1×14 ml# followed by evap!
oration and crystallization from hexane yielded 519 mg
"54)# of dark red microcrystals[ m[p[ 044Ð045>C "lit[
046Ð047>C ð7Ł#[ NMR "solvent CDCl2\ standard SiMe3#]
dH 6[20 "m\ 1H#\ 5[89 "m\ 1H#[
Crystal data for compounds 0\ 3 and 4\ along with
other experimental details\ are summarized in Table 2[
Single!crystal data collections were performed at ambient
temperature on a Rigaku AFC4S di}ractometer using
graphite
monochromatized
Mo Ka
radiation
Ä
"lꢁ9[60958 A#[ The unit cell parameters were determined
by least!squares re_nement of 14 carefully centered
re~ections[ Data reduction and subsequent calculations
were performed with teXsan for Windows ð04Ł[ The data
was corrected for Lorenz and polarization e}ects and for
absorption "PSI!scans ð05Ł#[
3[2[ Preparation of ðW"OC5H4Me!3#5Ł "2#
The structures were solved by direct methods using the
SIR81 ð06Ł program and full!matrix least!squares
re_nements on F1 were performed using the SHELXL!
86 ð07Ł program[ Non!hydrogen atoms were re_ned with
anisotropic displacement parameters and the hydrogen
atoms were included in the calculations at _xed distances
from their host atoms[ Figures were drawn with Ortep!2
for Windows ð08Ł[
3!MePhOAc "0[9 g\ 5[7 mmol# and ðW"eg#2Ł "9[25 g\
0[9 mmol# were dissolved in chlorobenzene\ and the reac!
tion solution was allowed to re~ux for eight hours[ The
solution was then _ltered and the _ltrate was washed
with NaOH!solution "09)\ 14 ml# and water "1×14 ml#[
Evaporation and crystallization from acetonitrile yielded
309 mg of dark red crystals "56)#[ m[p[ 029>C "lit[ 029Ð
Lehtonen, Ari
