Metallacrown Ethers
Organometallics, Vol. 22, No. 5, 2003 1083
3
2
8 Hz, | J (H5′H6′)| 2 Hz), 3.37 (m, H3 and H3′), 3.31 (m, H4
methane-d2): δ 69.86 (s, C3 and C4), 69.23 (d, C2, | J (PC)| 6
2
and H4′), 3.13 (m, H1 andH1′), 2.97 (m, H2 and H2′).
Hz), 68.26 (s, C5), 67.35 (s, C6), 65.74 (d, C1, | J (PC)| 12 Hz).
1H NMR (aliphatic protons, dichloromethane-d2): δ 4.08 (dd,
cis-Mo(CO)4{(2,2′-O2C12H 8)P (CH 2CH 2O)3-2-C12H 8-2′-P -
(2,2′-O2C12H8)}, 8. Solutions of 2.92 g (3.91 mmol) of Mo(CO)4-
(nbd) in 150 mL of degassed dichloromethane and 1.17 g (3.91
mmol) of 13 in 150 mL of degassed dichloromethane were
added simultaneously and dropwise to 300 mL of degassed
dichloromethane over a 2 h period. This mixture was stirred
for 30 min and then evaporated to dryness to give a brown
oil. The oil was triturated with methanol to yield 2.61 g (63.8%)
of crude 8 as an off-white powder. Recrystallization from a
dichloromethane/methanol mixture yielded analytically pure
8 as colorless crystals. Anal. Calcd for C46H36O11P2Mo: C,
57.87; H, 3.80. Found: C, 57.48; H, 3.79. 31P{1H} NMR
H6 and H6′, | J (H5H6) + 3J (H5H6′)| 8.9 Hz), 3.68 (dd, H5 and
3
3
3
H5′, | J (H5H6) + J (H5′H6′)| 8.9 Hz), 3.58 (m, H3, H3′, H4,
H4′), 3.42 (bs, H1, H1′, H2, H2′).
tr a n s-Mo(CO)4{(2,2′-C12H 8O2)P (CH 2CH 2O)3-2-C12H 8-2′-
P (2,2′-O2C12H8)}‚HgCl2, 17. A solution of 0.100 g (0.105 mmol)
of 8 in 1.2 mL of dichloromethane was prepared under nitrogen
at ambient temperature, and then 0.028 g (0.10 mmol) of solid
HgCl2 was added. The mixture was stirred overnight and then
was filtered through Celite and evaporated to dryness to yield
0.098 g (78.1%) of the crude 17 as a brown powder. Recrys-
tallization from a dichloromethane/hexanes mixture yielded
the analytically pure 17 as off-white crystals. Anal. Calcd for
2
(dichloromethane-d2): δ 172.28 (d, ArOP, | J (PP′)| 47 Hz),
169.60 (d, CH2OP, | J (PP′)| 47 Hz). 13C{1H} NMR (aliphatic
C46H36O13P2MoHgCl2 (plus 0.5 mol of C6H14): C, 46.35; H, 3.38;
2
carbons, dichloromethane-d2): δ 71.90 (s, C4), 71.73 (s, C3),
Cl, 5.59. Found: C, 46.43; H, 3.63; Cl, 5.83. 31P{1H} NMR-
2
2
70.98 (d, C2, | J (PC)| 7 Hz), 70.52 (s, C5), 68.99 (s, C6), 68.21
(chloroform-d): δ 190.67 (d, ArOP, | J (PP′)| 233 Hz), 174.09
2
2
(d, C1, | J (PC)| 7 Hz). 1H NMR (aliphatic protons, dichloro-
(d, CH2OP, | J (PP′)| 233 Hz). 13C{1H} NMR (aliphatic carbons,
2
3
2
methane-d2): δ 4.13 (ddd, H6, | J (H6H6′)| 11 Hz, | J (H6H5′)|
chloroform-d): δ 72.14 (s, C3 or C4), 70.34 (d, C2, | J (PC)| 5
3
8 Hz, | J (H6H5)| 2 Hz ), 3.93 (m, H1, H1′, and H6′), 3.65 (ddd,
Hz), 70.20 (s, C4 or C3), 69.75 (s, C5), 67.66 (s, C6), 67.18 (d,
C1, | J (PC)| 11 Hz). 1H NMR (aliphatic protons, chloroform-
2
3
3
2
H5, | J (H5H5′)| 11 Hz, | J (H5H6′)| 5 Hz, | J (H5H6)| 2 Hz), 3.51
m, H5′), 3.49 (m, H4 and H4′), 3.43 (m, H2 and H2′), 3.41 (m,
H3 and H3′).
d): δ 4.23 (m, H6), 4.05 (m, H6′, H1, and H5′), 3.95 (m, H1′),
3.88 (m, H5), 3.72 (m, H3 and H3′), 3.69 (m, H4 and H4′), 3.62
(m, H2 and H2′).
31P {1H} NMR Stu d y of th e HgCl2(s)-Ca ta lyzed cis-
tr a n s Isom er iza tion of cis-Mo(CO)4{P h 2P O(CH2CH2O)3-
2-C12H8-2′-OP P h 2}, 7. A solution of 0.011 g (0.012 mmol) of 7
in 0.6 mL of dichloromethane-d2 was prepared in a 5 mm,
screw-top NMR tube under nitrogen, and a 31P{1H} NMR
spectrum of the solution was recorded. Then solid HgCl2 (two
small crystals) was added to the solution. After vigorous
shaking, a nonquantitative 31P{1H} NMR spectrum was ac-
quired. The complex had completely converted to trans-Mo-
(CO)4{Ph2PO(CH2CH2O)3-2-C12H8-2′-OPPh2}, 14. 31P{1H} NMR
[cis-Mo(CO)4{P h 2P O(CH 2CH 2O)3-2-C12H 8-2′-OP P h 2}]2-
LiBP h 4, 18. A solution of 0.050 g (0.17 mmol) of LiBPh4‚3dme
and 0.15 g (0.17 mmol) of 7 in 8.4 mL of dichloromethane was
stirred for 2 h and then evaporated to dryness. The residue
was recrystallized from a dichloromethane/hexanes mixture
to give 0.14 g (68%) of analytically pure 18. Anal. Calcd for
[cis-Mo(CO)4{Ph2PO(CH2CH2O)3-2-C12H8-2′-OPPh2}]2LiBPh4:
C, 58.37; H, 4.19. Found: C, 58.50; H, 4.40. 31P{1H} NMR
(dichloromethane-d2): δ 150.22 (bs, ArOP), 145.50 (bs, CH2OP).
1H NMR (aliphatic protons, dichloromethane-d2): δ 4.03 (ddd,
2
(dichloromethane-d2): δ 161.05 (d, ArOP, | J (PP′)| 88 Hz),
2
3
3
2
H6, | J (H6H6′)| 11 Hz, | J (H6H5′)| 8 Hz, | J (H6H5)| 2 Hz), 3.95
(ddd, H6′, | J (H6′H6)| 11 Hz, | J (H6′H5)| 5 Hz, | J (H6′H5′)| 2
152.42 (d, CH2OP, | J (PP′)| 88 Hz).
2
3
3
31P {1H} NMR Stu d y of th e HgCl2(s)-Ca ta lyzed cis-
tr a n s Isom er iza tion of cis-Mo(CO)4{(2,2′-C12H8O2)P -
(CH2CH2O)3-2-C12H8-2′-P (2,2′-O2C12H8)}, 8. Meth od 1. A
solution of 0.057 g (0.060 mmol) of 8 in 0.6 mL of chloroform-d
was prepared in a 5 mm, screw-top NMR tube under nitrogen,
and the 31P{1H} spectrum of the solution was recorded. Then
one drop of a dilute, aqueous HgCl2 solution was added to the
surface of the NMR solution. Nonquantitative 31P{1H} NMR
spectra were acquired 2.5, 10, 20, 30, and 40 min and both
quantitive and nonquantitative 31P{1H} NMR spectra were
acquired 20 h after the addition. After 20 h, the ratio of
cis-Mo(CO)4{(2,2′-C12H8O2)P(CH2CH2O)3-2-C12H8-2′-P(2,2′-
O2C12H8)}, 8, to trans-Mo(CO)4{(2,2′-C12H8O2)P(CH2CH2O)3-
2-C12H8-2′-P(2,2′-O2C12H8)}, 15, was 0.21. 31P{1H} NMR for 15
2
3
Hz), 3.62 (ddd, H5, | J (H5H5′)| 11 Hz, | J (H5H6′)| 5 Hz,
3
2
3
| J (H5H6)| 2 Hz), 3.48 (ddd, H5′, | J (H5′H5)| 11 Hz, | J (H5′H6)|
3
8 Hz, | J (H5′H6′)| 2 Hz), 3.26 (m), 3.15 (m), 2.94 (m).
31P {1H} NMR Stu d y of th e Rea ction of Na BP h 4 w ith
cis-Mo(CO)4{P h 2P O(CH2CH2O)3-2-C12H8-2′-OP P h 2}, 7. A
0.002 g (0.006 mmol) sample of NaBPh4 was added to a
solution of 0.011 g (0.012 mmol) of 7 in 0.6 mL of dichloro-
methane-d2. The solution was stirred for 3 h, and then the
31P{1H} spectrum of the solution was obtained. 31P{1H} NMR
(dichloromethane-d2) major: δ 156.49 (vbs, ArOP), 148.76 (bd,
2
CH2OP, | J (PP′)| 35 Hz); minor (15): δ 161.91 (d, ArOP,
2
2
| J (PP′)| 86 Hz), 154.93 (d, CH2OP, | J (PP′)| 86 Hz).
31P {1H } NMR Tit r a t ion of cis-Mo(CO)4{P h 2P O(CH2-
CH2O)3-2-C12H8-2′-OP P h 2}, 7, w ith Li2(DMSO)2-µ-(DMSO)2-
(OH2)2(BP h 4)2. Solutions of 0.00894 g (0.0100 mmol) of 7 in
0.5 mL of dichloromethane-d2 and of 0.020 g (0.020 mmol) of
Li2(DMSO)2-µ-(DMSO)2(OH2)2(BPh4)2 in 0.5 mL of dichlo-
romethane-d2 were prepared. Aliquots of the solution of the
lithium salt were added to the solution of 7 using a 25 µL
syringe. Both 31P{1H} and 1H NMR spectra were taken after
each addition.
2
(chloroform-d): δ 190.44 (d, ArOP, | J (PP′)| 233 Hz), 173.09
2
(d, CH2OP, | J (PP′)| 233 Hz).
Meth od 2. A solution of 0.123 g (0.109 mmol) of 8 in 0.6
mL of chloroform-d was prepared in a 5 mm, screw-top NMR
tube under nitrogen, and the 31P{1H} spectrum of the solution
was recorded. Then solid HgCl2 (two small crystals) was added
to the solution. After vigorous shaking, nonquantitative 31P{1H}
NMR spectra were acquired every 10 min over a 1 h and 20
min period.
NMR Titr a tion of cis-Mo(CO)4{P h 2P O(CH2CH2O)3-2-
C
12H8-2′-OP P h 2}, 7, w ith LiBP h 4‚3d m e. Solutions of 0.00894
cis-Mo(CO)4{P h 2P O(CH 2CH 2O)3-2-C12H 8-2′-OP P h 2}‚
HgCl2, 16. A solution of 0.200 g (0.224 mmol) of 7 in 1.2 mL
of dichloromethane was prepared, and then HgCl2 (0.061 g,
0.224 mmol) was added. This mixture was stirred overnight
and then was filtered through Celite and evaporated to dryness
to yield 0.195 g (74.7%) of crude 16 as a dark yellow powder.
Recrystallization from a dichloromethane/hexanes mixture
yielded analytically pure 16 as an off-white solid. Anal. Calcd
for C46H44O9P2MoHgCl2 (with 0.33 mol of C6H14): C, 48.26; H,
3.77. Found: C, 48.25; H, 3.85. 31P{1H} NMR (dichloromethane-
g (0.0100 mmol) of 7 in 0.5 mL of dichloromethane-d2 and of
0.020 g (0.033 mmol) in 0.5 mL of LiBPh4‚3dme in dichloro-
methane-d2 were prepared, and 31P{1H} and H NMR spectra
1
of the solution were obtained. Aliquots of the solution of the
lithium salt were added to the solution of 7 using a 25 µL
syringe. Both 31P{1H} and 1H NMR spectra were taken after
each addition.
NMR Tit r a t ion of cis-Mo(CO)4{(2,2′-C12H 8O2)P (CH2-
CH2O)3-2-C12H8-2′-P (2,2′-O2C12H8)}, 10, w ith LiBP h 4‚3d m e.
Solutions of 0.00954 g (0.0100 mmol) of 8 in 0.5 mL of
dichloromethane-d2 and of 0.02 g (0.033 mmol) in 0.5 mL of
2
d2): δ 151.00 (d, ArOP, | J (PP′)| 39 Hz), 127.27 (d, CH2OP,
2
| J (PP′)| 40 Hz). 13C{1H} NMR (aliphatic carbons, dichloro-