the mixture was refluxed under N2 for 4 h, resulting in a change
from yellow to light brown. After cooling the solution was fil-
tered and the filtrate concentrated to ca. 2 cm3 in vacuo.
Deoxygenated diethyl ether (30 cm3) was added with stirring to
afford a light brown precipitate which was recrystallised from
CH2Cl2 and dried in vacuo. Yield 43 mg (24%) (Found: C, 21.8;
H, 3.5. Calc. for C12H24Cl2RuSe4: C, 21.9; H, 3.6%). Electro-
spray mass spectrum (MeCN): found m/z = 664, 623; calculated
for [102Ru35Cl([8]ane80Se2)2(MeCN)]ϩ m/z 666, [102Ru35Cl([8]-
ane80Se2)2]ϩ m/z = 625. UV/VIS spectrum (MeCN solution):
ture was refluxed under N2 for 3 h, resulting in a change from
green to yellow. After cooling to room temperature, NH4PF6
(60 mg, 0.36 mmol) was added and the solution volume reduced
to ca. 5 cm3 to give a yellow precipitate which was filtered off,
recrystallised from CH2Cl2 and dried in vacuo. Yield 65 mg,
(39%) (Found: C, 32.6; H, 3.6. Calc. for C30H39ClOsPSe4: C,
32.2; H, 3.5%). Electrospray mass spectrum (MeCN solution):
found m/z = 973; calculated for [190Os35Cl(PPh3)([16]ane80Se4)]ϩ
m/z = 975. 1H NMR spectrum (300 MHz, CD2Cl2, 298 K):
δ 7.9–7.3 (m, 15 H, PPh3) and 3.8–2.4 (m, CH2, 24 H). IR
spectrum (CsI disc): 3056w, 2928w, 1584w, 1481m, 1431m,
1357m, 1247w, 1089m, 999w, 841vs, 747m, 697s, 614w, 557s,
ν = 25 510 (εmol = 610 dm3 molϪ1 cmϪ1) and 23 365 (sh) cmϪ1
.
1H NMR spectrum (300 MHz, CD2Cl2, 298 K): δ 2.3–3.2 (m,
CH2). IR spectrum (CsI disc): 2974w, 2927w, 2880m, 1413m,
1357m, 1233w, 1101m, 1021w, 995w, 954w, 879w, 833m, 614w,
531s, 464m and 427w cmϪ1
.
532w, 298w, 244w and 220w cmϪ1
.
cis-[RuBr2([16]aneSe4)]. The compounds [16]aneSe4 (120
mg, 0.25 mmol), [Ru(dmf)6][CF3SO3]3 (210 mg, 0.21 mmol) and
LiBr (55 mg, 0.63 mmol) were added to deoxygenated EtOH
(75 cm3) and this mixture was refluxed under N2 for 4 h, during
which time a gradual change from yellow to brown was
observed. After cooling to room temperature the solution was
filtered and the filtrate evaporated to dryness. The resulting
brown solid was then washed with water prior to recrystallis-
ation from CH2Cl2. Yield 43 mg (27%) (Found: C, 19.4; H, 3.5.
Calc. for C12H24Br2RuSe4: C, 19.3; H, 3.2%). Electrospray mass
spectrum (MeCN): found m/z = 667; calculated for [102Ru79Br-
([16]ane80Se4)]ϩ m/z = 669. UV/VIS spectrum (MeCN solution):
ν = 19 650 (εmol = 190), 24 040 (330) and 41 670 cmϪ1 (14 910
dm3 molϪ1 cmϪ1). IR spectrum (CsI disc): 2965w, 2961w,
1430m, 1356m, 1261w, 1097m, 1028m, 863w, 799m and 393m
cis-RuCl2([16]aneSe4)]. Method as for cis-[RuCl2([8]aneSe2)2]
above, but using [16]aneSe4 (124 mg, 0.26 mmol) and [Ru-
(dmf)6]Cl3 in dmf (5.4 cm3, ca. 0.048 mol dmϪ3) giving a fawn
precipitate which was recrystallised from CH2Cl2 and dried
in vacuo. Yield 90 mg (54%) (Found: C, 22.0; H, 3.9. Calc. for
C12H24Cl2RuSe4: C, 21.9; H, 3.6%). Electrospray mass spectrum
(MeCN): found m/z = 663, 622; calculated for [102Ru35Cl([16]-
ane80Se4)(MeCN)]ϩ
m/z = 666,
[
102Ru35Cl([16]ane80Se4)]ϩ
m/z = 625. UV/VIS spectrum (MeCN solution): ν = 30 770 (sh,
1
εmol = 520) and 24 750 cmϪ1 (380 dm3 molϪ1 cmϪ1). H NMR
spectrum (300 MHz, CD2Cl2, 298 K): δ 2.2–3.4 (m, CH2). IR
spectrum (CsI disc): 2960w, 2915w, 1461m, 1432m, 1356m,
1283w, 1218w, 1097w, 1021w, 979w, 891m, 856w, 787w, 743m,
574w, 295w, 280w and 218w cmϪ1
.
cmϪ1
.
trans-[RuCl2([16]aneSe4)]. The compound cis-[RuCl2([16]-
aneSe4)] (20 mg, 0.030 mmol) was added to deoxygenated
MeNO2 (25 cm3). This solution was refluxed under N2 for 3 h,
cooled to room temperature and concentrated in vacuo. Diethyl
ether was then added to afford a brown solid which was filtered
off and dried in vacuo. Yield 12 mg (60%) (Found: C, 21.7; H,
3.5. Calc. for C12H24Cl2RuSe4: C, 21.9; H, 3.6%). Electrospray
mass spectrum (MeCN): found m/z = 664, 621; calculated for
trans-[RuBr2([16]aneSe4)]. Method as for trans-[RuCl2-
([16]aneSe4)] above, but using cis-[RuBr2([16]aneSe4)], giving a
brown precipitate. Yield 30 mg (19%) (Found: C, 19.1; H, 3.0.
Calc. for C12H24Br2RuSe4: C, 19.3; H, 3.2%). Electrospray mass
spectrum (MeCN): found m/z = 667; calculated for [102Ru79Br-
([16]ane80Se4)]ϩ m/z = 669. UV/VIS spectrum (MeCN solution):
ν = 24 750 (εmol = 120) and 20 410 cmϪ1 (70 dm3 molϪ1 cmϪ1).
1H NMR spectrum (90 MHz, CD2Cl2, 300 K): δ 2.1–3.6 (m,
CH2). IR spectrum (CsI disc): 2966w, 2919w, 1427m, 1398m,
1357m, 1280w, 1243w, 1216w, 1102w, 982w, 887w, 833w, 790w
[
102Ru35Cl([16]ane80Se4)(MeCN)]ϩ m/z = 666, 102Ru35Cl([16]-
[
ane80Se4)]ϩ m/z = 625. UV/VIS spectrum (MeCN solution):
ν = 33 330 (εmol = 3260) and 27 470 cmϪ1 (960 dm3 molϪ1 cmϪ1).
IR spectrum (CsI disc): 2960w, 2915w, 1461m, 1360m, 1245w,
1218w, 1080w, 979w, 891w, 856w, 787w, 750w, 580w and 310w
and 573w cmϪ1
.
trans-[RuI2([16]aneSe4)]. Method as for cis-[RuBr2-
([16]aneSe4)] above, but using [16]aneSe4 (155 mg, 0.32 mmol),
[Ru(dmf)6][CF3SO3]3 (250 mg, 0.25 mmol) and NaI (115 mg,
0.76 mmol). Yield 38 mg (18%) (Found: C, 17.6; H, 3.1. Calc.
for C12H24I2RuSe4: C, 17.2; H, 2.9%). Electrospray mass spec-
trum (MeCN): found m/z = 715; calculated for [102Ru127I-
([16]ane80Se4)]ϩ m/z = 717. UV/VIS spectrum (MeCN solution):
ν = 43 860 (εmol = 1942), 41 150 (1120), 34 840 (480) and 27 860
cmϪ1 (170 dm3 molϪ1 cmϪ1). IR spectrum (CsI disc): 2960w,
2921w, 1423m, 1357m, 1315w, 1246w, 1096m, 983w, 834w,
cmϪ1
.
trans-[RuCl(PPh3)([16]aneSe4)]PF6. The compounds [16]-
aneSe4 (60 mg, 0.12 mmol) and [RuCl2(PPh3)3] (118 mg, 0.12
mmol) were added to deoxygenated MeOH (60 cm3). The
mixture was refluxed under N2 for 3.5 h, resulting in a change
to yellow, and then left to stir at room temperature for 16 h.
The salt NH4PF6 (60 mg, 0.36 mmol) was then added and the
solution volume reduced to ca. 5 cm3 to give a yellow precipi-
tate which was filtered off, recrystallised from CH2Cl2 and
dried in vacuo. Yield 80 mg (63%) (Found: C, 34.8; H, 3.6.
Calc. for C30H39ClPRuSe4: C, 34.9; H, 3.8%). FAB mass spec-
614w and 510w cmϪ1
.
trans-[RuBr2([16]aneSe4)]Br.
The
compound
trans-
trum: found m/z = 883, 621; calculated for
[
102Ru35Cl-
[RuBr2([16]aneSe4)] (40 mg, 0.05 mmol) was added to MeCN
(5 cm3) followed by Br2–CCl4 (5 drops) with stirring, pro-
ducing a change from brown to dark green. The solution was
concentrated to ca. 2 cm3 and diethyl ether (10 cm3) added to
afford a green solid which was filtered off and dried in vacuo.
Yield 15 mg (34%) (Found: C, 17.1; H, 3.2. Calc. for
C12H24Br3RuSe4: C, 17.4; H, 2.9%). Electrospray mass spec-
trum (MeCN): found m/z = 745, 666; calculated for
(PPh3)([16]ane80Se4)]ϩ m/z = 887, 102Ru35Cl([16]ane80Se4)]ϩ
[
m/z = 625. UV/VIS spectrum (CH2Cl2 solution): ν = 28 090
(εmol = 583) and 25 000 cmϪ1 (sh, 340 dm3 molϪ1 cmϪ1). 1H
NMR spectrum (300 MHz, CD2Cl2, 298 K): δ 7.7–7.3 (m, 15
H, PPh3) and 3.3–1.7 (m, CH2, 24 H). IR spectrum (CsI disc):
3053m, 2922w, 2848w, 1584w, 1480m, 1432m, 1407m, 1248m,
1185w, 1161w, 1087m, 1025w, 999w, 984w, 838vs, 799m, 742m,
695m, 557s, 529s, 497w, 465w, 440w, 421w, 351w and 269w
[
102Ru79Br2([16]ane80Se4)]ϩ m/z = 748, [102Ru79Br([16]ane80Se4)]ϩ
cmϪ1
.
m/z = 669. UV/VIS spectrum (MeCN solution): ν = 26 660
(εmol = 1550), 22 200 (sh) and 15 340 cmϪ1 (830 dm3 molϪ1
cmϪ1). IR spectrum (CsI disc): 2917w, 1420m, 1356m, 1287w,
1250w, 1222w, 1106w, 982w, 884w, 833w, 789w, 741w, 532w
trans-[OsCl(PPh3)([16]aneSe4)]PF6. The compounds [16]-
aneSe4 (75 mg, 0.15 mmol) and [OsCl2(PPh3)3] (161 mg, 0.15
mmol) were added to deoxygenated EtOH (70 cm3). The mix-
and 240w cmϪ1
.
J. Chem. Soc., Dalton Trans., 1997, Pages 3719–3724
3723
Levason, William
