Tin"IV# and organotin"IV# complexes containing mono or bidentate N!donor ligands
3378
pound 0[ Yield] 69)\ m[p[ 43Ð45>C "Found] C\ 21[3^ 173 m\ 163
m
ðn"SnÐCl#Ł[ "acetone\ 14>C\
L
0[0×09−2 M#] 13[2 V−0 cm1 mol−0
[
H\ 4[1^ N\ 05[5[ Calc[ for C8H06ClN3Sn] C\ 21[1^ H\
4[0^ N\ 05[6)#[ NMR "Acetone!d5#] 0H\ d 09[7 "br\
1H\ NÐH#\ 6[71 "s\ 1H\ 1!CH#\ 6[02 "s\ 3H\ 3!\ 4!CH#\
9[55 ð=1J"008SnÐH#=ꢁ69[7 Hz\ =1J"006SnÐH#=ꢁ56[7 Hz\
s\ 8H\ SnCH2Ł^ 008Sn\ d −72[4 ppm[ IR] 2051 w\ 2099
w ðn"CÐH#Ł\ 438 s ðn"SnÐC#Ł[ L "acetone\ 14>C\
ðTrichlorophenylbis"imidazole#tin"IV#Ł "4#[ Com!
pound 4 was prepared similarly to compound 3[ Yield]
36)\ m[p[ 017Ð021>C "Found] C\ 22[9^ H\ 2[1^ N\
01[5[ Calc[ for C01H02Cl2N3Sn] C\ 21[8^ H\ 2[9^ N\
01[7)#[ NMR "Acetone!d5#] 0H\ d 01[2 "br\ 1H\ NÐ
H#\ 7[63\ 7[56 "br\ 1H\ 1!CH#\ 6[43 "br\ 3H\ 3! and 4!
CH#\ 7[1\ 6[8\ 6[7\ 6[4\ 6[2 "m\ 4H\ SnÐC5H4#[ IR] 2023
w ðn"CÐH#Ł\ 351 m ðd"Ph#Ł\ 207 br\ 209 m\ 175 m\ 169
m\ 159 m ðn"SnÐC# and n"SnÐCl#Ł[ L "acetone\ 14>C\
0[0×09−2 M#] 0[3 V−0 cm1 mol−0
[
ðTriphenylbis"imidazole#tin"IV#Łchloride "1#[ To a
stirred refrigerated "9>C# diethyl ether solution
"099 cm2# of imidazole "L0# "161 mg\ 3[9 mmol#\
"C5H4#2SnCl "274 mg\ 0[9 mmol# was added under N1
stream[ The mixture was stored at 9>C and stirred
for 01 h[ A white precipitate was formed\ which was
_ltered o}\ washed with diethyl ether "2×19 cm2#\
dried in vacuo to constant weight "19>C\ ca[ 9[0 Torr#
and shown to be compound 1[ Yield] 28)\ m[p[ 044Ð
046>C "Found] C\ 44[9^ H\ 3[1^ N\ 09[3[ Calc[ for
C13H12ClN3Sn] C\ 44[2^ H\ 3[3^ N\ 09[6)#[ NMR
"Acetone!d5#] 0H\ d 6[73 ð=1J"008SnÐH#=ꢁ58[9 Hz\ =1J"
006SnÐH#=ꢁ55[2 Hz\ d\ 1H\ Sn!o!C5H4#Ł\ 6[70 ð=1J"
008SnÐH#=ꢁ56[0 Hz\ =1J"006SnÐH#=ꢁ53[1 Hz\ d\ 1H\
Sn!o!C5H4#Ł\ 6[41 "s\ 1H\ 1!CH#\ 6[32 "m\ 5H\ Sn!m!\
0[0×09−2 M#] 30[9 V−0 cm1 mol−0
[
ðChlorotriphenyl"benzimidazole#tin"IV#Ł "5#[ To a
stirred diethyl ether solution "099 cm2# of benzi!
midazole "L1# "125 mg\ 1[9 mmol#\ "C5H4#2SnCl
"274 mg\ 0[9 mmol# in dichloromethane "19 cm2# was
added at 39>C[ A colorless precipitate was formed
immediately\ which was _ltered o} after 5 h\ washed
with diethyl ether "2×19 cm2#\ dried in vacuo to con!
stant weight "19>C\ ca[ 9[0 Torr# and shown to be
compound 5[ Yield] 39)\ m[p[ 038Ð041>C "Found]
C\ 48[4^ H\ 3[3^ N\ 4[7[ Calc[ for C14H10ClN3Sn] C\
48[5^ H\ 3[1^ N\ 4[5)#[ NMR "Acetone!d5#] 0H\ d 7[95
"s\ 0H\ 1!CH#\ 6[72 ð=1J"008SnÐH#=ꢁ54[9 Hz\ d\ 5H\
Sn!o!C5H4#Ł\ 6[39Ð6[44 "m\ 00H\ Sn!m!\ Sn!p!C5H4
and 3! and 6!CH#\ 6[06 "m\ 1H\ 4! and 5!CH#[ IR]
2259 br ðn"NÐH#Ł\ 2046 w\ 2018 w ðn"CÐH#Ł\ 344 s\ 315
s\ 311 sh ðd"Ph#Ł\ 189 m ðn"SnÐC#Ł\ 115 s ðn"SnÐCl#Ł[ L
Sn!p!C5H4#\ 5[86 "s\ 3H\ 3!\ 4!CH#^ 008Sn\
−114 ppm[ IR] 2020 w\ 2938 w ðn"CÐH#Ł\ 352 s\ 342 s
ðd"Ph#Ł\ 189 ðn"SnÐC#Ł[ "acetone\ 14>C\
0[9×09−2 M#] 1[5 V−0 cm1 mol−0
d
m
L
[
ðTrichloromethylbis"imidazole#tin"IV#Ł=H1O "2#[ To
a stirred diethyl ether:ethanol "0:0# solution "099 cm2#
of imidazole "L0# "161 mg\ 3[9 mmol#\ "CH2#SnCl2
"139 mg\ 0[9 mmol# was added at room temperature[
The mixture was stirred for 01 h[ The solvent was
removed with a rotary evaporator and diethyl ether:
petroleum ether 0]0 were added until an oil was
formed\ which was separated from the solution[ The
oily residue was washed with diethyl ether:petroleum
ether 0]0 "2×19 cm2#\ dried in vacuo to constant
weight "19>C\ ca[ 9[0 Torr# and shown to be com!
pound 2[ Yield] 64) "Found] C\ 10[5^ H\ 2[4^ N\ 03[5[
Calc[ for C6H02Cl2N3OSn] C\ 10[2^ H\ 2[2^ N\ 03[1)#[
NMR "CD2OD#] 0H\ d 7[60 s "1H\ 1!CH#\ 6[49 s "3H\
3! and 4!CH#\ 0[10 s\ 2H\ SnCH2Ł[ IR] 2399 br ðn"OÐ
H#Ł\ 2039 w\ 2092 w ðn"CÐH#Ł\ 458 sh br ðn"SnÐC#Ł\ 176
m\ 164 m ðn"SnÐCl#Ł[ L "acetone\ 14>C\ 0[9×09−2 M#]
"acetone\ 14>C\ 9[8×09−2 M#] 0[2 V−0 cm1 mol−0
[
ðDichlorodimethylbis"benzimidazole#tin"IV#Ł "6#[ To
a stirred dichloromethane solution "099 cm2# of benz!
imidazole "L1# "362 mg\ 3[9 mmol#\ "CH2#1SnCl1
"119 mg\ 0[9 mmol# was added at room temperature[
A colorless precipitate was formed immediately\
which was _ltered o} after 5 h\ washed with dichlo!
romethane "2×19 cm2#\ dried in vacuo to constant
weight "19>C\ ca[ 9[0 Torr# and shown to be com!
pound 6[ Yield] 87)\ m[p[ 060Ð063>C "Found] C\
31[1^ H\ 3[9^ N\ 01[1[ Calc[ for C05H07Cl1N3Sn] C\ 31[0^
H\ 3[9^ N\ 01[2)#[ NMR "Acetone!d5#] 0H\ d 00[0 "br\
1H\ NÐH#\ 7[66 "s\ 1H\ 1!CH#\ 6[71 "m\ 3H\ 3! and 6!
CH#\ 6[28 "m\ 3H\ 4! and 5!CH#\ 0[11 ð=1J"008SnÐ
H#=ꢁ81[0 Hz\ =1J"006SnÐH#=ꢁ76[8 Hz\ s\ 5H\ SnCH2Ł^
008Sn\ d −036[1 ppm[ IR] 2049 br ðn"NÐH#Ł\ 2023 w
ðn"CÐH#Ł\ 462 s ðn"SnÐC#Ł\ 324 s\ 311 s ðd"Ph#Ł\ 117 s
08[6 V−0 cm1 mol−0
[
ðn"SnÐCl#Ł[
L
"acetone\ 14>C\ 9[8×09−2 M#]
[
24[7 V−0 cm1 mol−0
ðTrichlorobutylbis"imidazole#tin"IV#Ł "3#[ To a stir!
red diethyl ether solution "099 cm2# of imidazole "L0#
"161 mg\ 3[9 mmol#\ "C3H8#SnCl2 "453 mg\ 1[9 mmol#
was added at room temperature[ A colorless pre!
cipitate was formed immediately\ which was _ltered
o} after 5 h\ washed with diethyl ether "2×19 cm2#\
dried in vacuo to constant weight "19>C\ ca[ 9[0 Torr#
and shown to be compound 3[ Yield] 84)\ m[p[ 82Ð
84>C "Found] C\ 17[6^ H\ 3[1^ N\ 02[2[ Calc[ for
C09H06Cl2N3Sn] C\ 17[6^ H\ 3[0^ N\ 02[3)#[ NMR
"Acetone!d5#] 0H\ d 01[1 "br\ 1H\ NÐH#\ 7[69 "br\ 1H\
1!CH#\ 6[49 "br\ 3H\ 3! and 4!CH#\ 0[5Ð0[7 "m\ 3H\
SnÐC3H8#\ 0[21 "ps\ 1H\ SnÐC3H8#\ 9[74 "t\ 2H\ SnÐ
ðDichlorodiphenylbis"benzimidazole#tin"IV#Ł "7#[ To
a stirred dichloromethane:diethyl ether "1:0# solution
"099 cm2# of benzimidazole "L1# "362 mg\ 3[9 mmol#\
"C5H4#1SnCl1 "233 mg\ 0[9 mmol# was added at room
temperature[ A pale brown precipitate was formed
immediately\ which was _ltered o} after 5 h\ washed
with diethyl ether "2×19 cm2#\ dried in vacuo to con!
stant weight "19>C\ ca[ 9[0 Torr# and shown to be
compound 7[ Yield] 78)\ m[p[ 051Ð053>C "Found]
C\ 42[5^ H\ 2[8^ N\ 8[8[ Calc[ for C15H11Cl1N3Sn] C\
42[7^ H\ 2[7^ N\ 8[6)#[ NMR "Acetone!d5#] 0H\ d 09[9
"br\ 1H\ NÐH#\ 7[30 "s\ 1H\ 1!CH#\ 6[87 ð=1J"008SnÐ
C3H8#[ IR] 2015 m\ 2936 w ðn"CÐH#Ł\ 507 m ðn"SnÐC#Ł\ H#=ꢁ097[3 Hz\ =1J"006SnÐH#=ꢁ096[6\ d\ 3H\ Sn!o!