1
4.13%. Λ 62 cm2 ΩϪ1 molϪ1. IR (KBr): ν(CN) 2320, 2291,
ν(RuH) 2049, ν(CO) 1935 cmϪ1. NMR (CD2Cl2): δH (400 MHz)
2.30, 2.29 (3 H each, both s, CH3CN), Ϫ14.19 [1 H, t, J(P,H)
18.8, RuH]; δC (100.6 MHz) 203.7 [t, J(P,C) 13.4, CO], 126.0,
125.3 (both s, CN), 3.4, 3.1 (both s, CH3CN); δP (162.0 MHz)
51.8 (s, PiPr3), Ϫ144.4 [sept, J(P,F) 709.5, PF6Ϫ].
portions of pentane and dried. The H and 31P NMR spectra
revealed the presence of the carbene complex 22 (ca. 80%), the
phosphonium salt 16 (ca. 10%) and some by-products which
could not be separated by fractional crystallisation. If the time
for the reaction was increased to 20 min, compound 16 became
the dominating species. Data for 22: NMR (CD2Cl2): δH (200
MHz) 17.31 [1 H, q, J(H,H) 6.5, Ru᎐CH], 2.90 [3 H, d,
᎐
[RuH(ꢀ2-O2CCH3)(CO)(PCy3)2], 19. A solution of 2 (80 mg,
0.11 mmol) in THF (8 cm3) was treated with potassium acetate
(150 mg, 1.53 mmol) and stirred for 30 min at room temper-
ature. The solvent was evaporated in vacuo, the residue was
extracted twice with 7 cm3 portions of benzene, and the com-
bined extracts were brought to dryness in vacuo. The remaining
white solid was washed twice with 2 cm3 portions of pentane
and dried; yield 77 mg (91%); mp 61 ЊC (decomp.). Found: C,
62.28; H, 9.50. C39H70O3P2Ru requires: C, 62.46; H, 9.41%. IR
(KBr): ν(RuH) 2052, ν(CO) 1899, ν(OCO)asym 1549, ν(OCO)sym
1447 cmϪ1. NMR (C6D6): δH (400 MHz) 2.23–1.25 (69 H, br m,
C6H11 and O2CCH3), Ϫ17.40 [1 H, t, J(P,H) 19.7, RuH]; δC
(100.6 MHz) 207.8 (br s, CO), 181.7 (s, O2CCH3), 24.7 (s,
O2CCH3); δP (81.0 MHz) 46.4 (s).
J(H,H) 6.5, ᎐CHCH ], 2.11–1.26 (69 H, br m, C H and
᎐
3
6
11
O2CCH3); δP (81.0 MHz) 46.5 (s).
[RuCl(CH᎐CH )(CO) (PiPr ) ], 23. A slow stream of CO
᎐
2
2
3 2
was passed for 30 s through a solution of 3 (80 mg, 0.16 mmol)
in hexane (8 cm3) at room temperature. A change of colour
from red to pale yellow occurred. The solvent was evaporated
in vacuo, the remaining off-white solid was washed twice with
3 cm3 portions of pentane (0 ЊC) and dried in vacuo; yield 78 mg
(88%); mp 106 ЊC (Found: C, 48.74; H, 8.64. C22H45ClO2P2Ru
requires: C, 48.93; H, 8.40%. IR (KBr): ν(CO) 2012, 1942,
ν(C᎐C) 1559 cmϪ1. NMR (C6D6): δH (400 MHz) 8.24 [1 H, dd,
᎐
J(H,H) 19.6, J(H,H) 11.7 RuCH], 6.44 [1 H, dd, J(H,H) 11.7,
J(H,H) 2.9, one H of ᎐CH cis to RuCH], 5.88 [1 H, dd, J(H,H)
᎐
2
19.6, J(H,H) 2.9, one H of ᎐CH trans to RuCH]; δ (100.6
MHz) 201.5 [t, J(P,C) 11.0, CO], 197.2 [t, J(P,C) 9.1, CO], 166.4
᎐
2
C
[Ru(CH᎐CH )(ꢀ2-O CCH )(CO)(PCy ) ], 20. Method A. A
᎐
2
2
3
3 2
slow stream of acetylene was passed through a solution of 19
(38 mg, 0.05 mmol) in benzene (1 cm3) for 15 min. After the
solution was stirred under an atmosphere of acetylene for 4 h,
[t, J(P,C) 12.4, RuCH], 124.2 (s, RuC᎐C); δ (162.0 MHz)
35.9 (s).
᎐
P
1
the solvent was evaporated in vacuo. The H NMR spectrum
Reaction of compound 23 with HBF4. A solution of 23 (86 mg,
0.16 mmol) in CH2Cl2 (5 cm3) was treated with a 1.6 M solution
of HBF4 in diethyl ether (0.15 cm3, 0.24 mmol) at room tem-
perature. After the solution was stirred for 5 min, the solvent
was evaporated in vacuo, the residue was washed twice with
revealed that a mixture of 19 : 20 in the ratio of 9 : 1 was
obtained, which could not be separated by fractional
crystallisation.
Method B. A solution of 6 (90 mg, 0.12 mmol) in THF (14
cm3) was treated with potassium acetate (250 mg, 2.55 mmol)
and stirred for 20 min at room temperature. The solvent was
evaporated in vacuo, the residue was extracted twice with 7 cm3
portions of benzene, and the combined extracts were brought
to dryness in vacuo. The remaining off-white solid was washed
twice with 2 cm3 portions of pentane (0 ЊC) and dried; yield 89
mg (92%); mp 194 ЊC (Found: C, 63.30; H, 8.89. C41H72O3P2Ru
1
5 cm3 portions of pentane and dried. The H and 31P NMR
spectra revealed that besides the phosphonium salt 15 (ca. 80%)
some by-products were formed which could not be identified
and not be separated from 15 by fractional crystallisation.
[Ru(CH᎐CH )(CO)(NCCH ) (PCy ) ]PF , 24a. This com-
᎐
2
3
2
3
2
6
pound was prepared as described for 18b, from 6 (119 mg,
0.16 mmol), KPF6 (100 mg, 0.54 mmol) and acetonitrile (2 cm3,
0.04 mol) in CH2Cl2 (8 cm3) at room temperature. Off-white
solid: yield 113 mg (75%); mp 142 ЊC (decomp.). Found: C,
54.47; H, 7.79; N, 2.78. C43H75F6N2OP3Ru requires: C, 54.71;
H, 8.01; N, 2.97%. Λ 62 cm2 ΩϪ1 molϪ1. IR (KBr): ν(CN) 2322,
requires: C, 63.46; H, 9.35%. IR (KBr): ν(CO) 1900, ν(C᎐C)
᎐
1612, ν(OCO)asym 1552, ν(OCO)sym 1446 cmϪ1. NMR (C6D6): δH
(200 MHz) 8.46 [1 H, dd, J(H,H) 16.5, J(H,H) 9.1, RuCH], 5.99
[1 H, dd, J(H,H) 9.1, J(H,H) 1.8, one H of ᎐CH cis to RuCH],
᎐
2
5.47 [1 H, dd, J(H,H) 16.5, J(H,H) 1.8, one H of ᎐CH trans to
᎐
2
RuCH], 2.36–1.25 (69 H, br m, C6H11 and O2CCH3); δC (100.6
MHz) 209.6 [t, J(P,C) 14.2, CO], 181.4 (s, O2CCH3), 164.6 [t,
2291, ν(CO) 1939, ν(C᎐C) 1558 cmϪ1. NMR (CD2Cl2): δH (400
᎐
MHz) 7.19 [1 H, dd, J(H,H) 17.1, J(H,H) 7.5, RuCH], 5.54
J(P,C) 11.2, RuCH], 118.8 (s, RuC᎐C), 22.7 (s, O CCH ); δ
[1 H, br d, J(H,H) 7.5, one H of ᎐CH cis to RuCH], 5.08 [1 H,
᎐
2
᎐
2
3
P
(162.0 MHz) 28.4 (s).
d, J(H,H) 17.1, one H of ᎐CH trans to RuCH], 2.52–1.25 (72
᎐
2
H, br m, C6H11 and CH3CN); δC (100.6 MHz) 206.2 [t, J(P,C)
13.7, CO], 153.3 (br s, RuCH), 128.3, 127.3 (both s, CN), 123.4
[Ru(CH᎐CHPh)(ꢀ2-O CCH )(CO)(PCy ) ], 21. A solution
᎐
2
3
3 2
of 19 (83 mg, 0.11 mmol) in benzene (12 cm3) was treated
dropwise with phenylacetylene (0.07 cm3, 0.65 mmol) and
stirred for 4 h at room temperature. The solvent was evaporated
in vacuo, the off-white residue was washed with pentane (2 cm3;
(s, RuC᎐C), 4.3, 3.1 (both s, CH CN); δ (162.0 MHz) 23.4 (s,
᎐
3
P
PCy3), Ϫ144.4 [sept, J(P,F) 710.6, PF6Ϫ].
[Ru(CH᎐CH )(CO)(NCCH ) (PCy ) ]BPh , 24b. A suspen-
᎐
2
3
2
3
2
4
1
Ϫ78 ЊC) and dried. The H NMR spectrum revealed that a
sion of 24a (113 mg, 0.12 mmol) in methanol (10 cm3) was
treated with NaBPh4 (250 mg, 0.73 mmol) and stirred for 1 h at
room temperature. The solvent was evaporated in vacuo, the
residue was washed twice with 8 cm3 portions of methanol and
then dissolved in CH2Cl2 (10 cm3). The solution was filtered and
the filtrate was brought to dryness in vacuo. A light red solid
was obtained, which was washed twice with 6 cm3 portions of
pentane and dried; yield 90 mg (67%); mp 114 ЊC (decomp.).
Found: C, 71.68; H, 8.05; N, 2.53. C67H95BN2OP2Ru requires:
C, 71.96; H, 8.56; N, 2.51%. Λ 39 cm2 ΩϪ1 molϪ1. IR (KBr):
mixture of 21 (ca. 90%) and a by-product was obtained, the
latter of which could not be exactly identified and not separated
by fractional crystallisation. Data for 21: IR (KBr): ν(CO)
1900, ν(C᎐C) 1596, ν(OCO)
1552, ν(OCO)sym 1446 cmϪ1
.
᎐
asym
NMR (C6D6): δH (400 MHz) 9.17 [1 H, d, J(H,H) 15.3, RuCH],
7.22 (5 H, m, C H ), 6.65 [1 H, d, J(H,H) 15.3, ᎐CHPh], 2.40–
᎐
6
5
1.18 (69 H, br m, C6H11 and O2CCH3); δC (100.6 MHz) 209.5 [t,
J(P,C) 14.2, CO], 181.7 (s, O2CCH3), 161.4 [t, J(P,C) 11.2,
RuCH], 133.6, 130.6, 128.8, 128.3, 124.1, 123.8 (all s, C6H5 and
RuC᎐C), 22.7 (s, O CCH ); δ (162.0 MHz) 32.8 (s).
ν(CN) 2305, 2275, ν(CO) 1942, ν(C᎐C) 1580 cmϪ1. NMR
᎐
᎐
2
3
P
(CD2Cl2): δH (400 MHz) 7.34–6.86 (21 H, br m, C6H5 and
Reaction of compound 20 with HBF4. A solution of 20 (57 mg,
0.07 mmol) in CH2Cl2 (4 cm3) was treated at 0 ЊC with a 1.6 M
solution of HBF4 in diethyl ether (0.25 cm3, 0.40 mmol). After
the solution was stirred for 2 min at 0 ЊC, the solvent was
evaporated in vacuo, the residue was washed twice with 5 cm3
RuCH), 5.41 (1 H, br m, one H of ᎐CH cis to RuCH), 5.00
᎐
2
[1 H, d, J(H,H) 17.0, one H of ᎐CH trans to RuCH], 2.27–1.26
᎐
2
(72 H, br m, C6H11 and CH3CN); δC (100.6 MHz) 205.8 (br s,
CO), 164.2 [q, J(B,C) 49.5, ipso-C of BC6H5], 136.0 (s, CH of
BC6H5), 128.4, 127.3 (both s, CN), 125.7 [q, J(B,C) 3.0, CH of
D a l t o n T r a n s . , 2 0 0 4 , 3 7 5 – 3 8 3
381