Some insertion reactions of the Mn-C bond of cyclomanganated triphenylphosphine chalcogenides

Article abstract of DOI:10.1016/S0022-328X(97)00474-9

The complex Ph₂P((CO)₄ (1b) reacts with alkenes CH₂=CH-R (R=COOMe, CN, C(O)Me) in refluxing MeCN or MeOH to give substituted derivatives of Ph₃P=S with a CH₂CH₂R group introduced in the ortho position of one phenyl ring. Other species are also formed including 3-cyano-4-(2-diphenylthiophosphinyl)phenyl)-2-buten-2-amine (characterised by an X-ray structure determination) from the reaction of 1b with CH₂=CHCN in MeCN. In contrast, reaction with alkynes C₂(COOMe)₂ or C₂H(COOMe) allowed isolation of the new seven-membered metallocycle arising from insertion of the alkyne into the Mn-C bond of 1b. All three Ph₂P((CO)₄ (E=O, S, Se) readily insert SO₂; a structure determination of the product with E=Se shows a six-membered metallocyclic ring which incorporates five different elements.

Full text of DOI:10.1016/S0022-328X(97)00474-9

Ž
.
Journal of Organometallic Chemistry 155 1998 281–291
Some insertion reactions of the Mn–C bond of cyclomanganated
1
triphenylphosphine chalcogenides
)
Gary J. Depree, Lyndsay Main, Brian K. Nicholson
School of Science and Technology, UniÕersity of Waikato, PriÕate Bag 3105, Hamilton, New Zealand
Received 23 April 1997
Abstract
Ž
.
Ž
Ž .
.
The complex
1b reacts with alkenes CH2 5CH–R RsCOOMe, CN, C O Me in refluxing MeCN or MeOH
to give substituted derivatives of Ph3P5S with a CH2CH2R group introduced in the ortho position of one phenyl ring. Other species are
Ž
.
.
Ž
.
also formed including 3-cyano-4- 2-diphenylthiophosphinyl phenyl -2-buten-2-amine characterised by an X-ray structure determination
Ž
.
Ž
.
from the reaction of 1b with CH2 5CHCN in MeCN. In contrast, reaction with alkynes C2 COOMe or C2H COOMe allowed isolation
2
of the new seven-membered metallocycle arising from insertion of the alkyne into the Mn–C bond of1b. All
Ž
.
three
EsO, S, Se readily insert SO2; a structure determination of the product with EsSe shows a
six-membered metallocyclic ring which incorporates five different elements. q 1998 Elsevier Science S.A.
Keywords: Insertion reactions; Cyclomanganated triphenylphosphine chalcogenides; Metallocyclic ring
1. Introduction
are assumed to occur via initial insertion of the unsatu-
rated substrate into the Mn–C bond, although only in
the cases of the reactions of orthomanganated triph-
We have recently described orthomanganated com-
w
x
enylphosphite with alkynes 5a,5b , and the reactions of
plexes of type 1 derived from triphenylphosphine
w x
orthomanganated aryl ketones with SO2 6 , have the
2
w x
Ž
.
chalcogenides 1 . These contain a Mn–C sp bond of
the type which has been shown to be a reactive site for
reactions of alkenes, alkynes and other unsaturated
species with cyclomanganated compounds derived from
initial insertion products been isolated. More usually
further reactions occur, leading ultimately to organic
products with loss of the manganese.
Complexes 1 have the organic ligand attached firmly
to the manganese via the chalcogen atom, as shown for
w
x
aryl ketones 2,3a,3b,3c,3d,3e,3f,3g,3h , from a, b-un-
w
x
saturated ketones 2,4a,4b and from triphenylphosphite
Ž
.
example by the reaction of 1b with P OMe in which
3
w
x
5a,5b . These reactions give new compounds via spe-
cific activation at the metallated carbon atom, and most
up to two CO ligands are displaced rather than the
w x
S-donor atom 1 . These are therefore potential sub-
strates for examining insertion reactions in more detail
since the resulting compounds should retain the ligand
coordinated to the metal. The reactions are of additional
interest since they provide a route to ortho-functiona-
lised compounds that could not be prepared readily
from the free ligand.
)
Corresponding author.
1 Dedicated to Professor Peter M. Maitlis on the occasion of his
65th birthday.
This present paper describes reactions of the or-
thomanganated complexes 1 with alkenes, alkynes and
0022-328Xr98r$19.00 q 1998 Elsevier Science S.A. All rights reserved.

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)
282
G.J. Depree et al.rJournal of Organometallic Chemistry 155 1998 281–291
Ž
.
Ž
.
with SO2. Most of the chemistry is developed with the
sulfide 1b, since this is the example which can be most
chalcogenide ;0.22 mmol and alkene ;0.3 mmol
Ž
.
were dissolved in the solvent 20 mL and the solution
was degassed. The mixture was refluxed under nitrogen
for periods ranging from 2 h to several days, with the
extent of reaction being monitored by t.l.c. At the
completion of reaction the solvent was removed under
vacuum and the residue chromatographed. Only major
bands were extracted and products are reported in order
of increasing polarity.
w x
efficiently prepared 1 .
2.1.1. Reactions of orthomanganated triphenylphos-
phine sulfide with butenone
Ž
Ž
.
Ž
.
2.1.1.1. In acetonitrile. Ph2 P
CO
1b
4
Ž
.
Ž
100 mg, 0.218 mmol and butenone 0.025 mL, 0.300
.
mmol were refluxed in acetonitrile for 2 h. The residue
Ž .
Ž
.
was chromatographed PLC, CH2Cl2 to give:
. Ž .
mg, 12% ; ii 4- 2-diphenyl-
i
Ž
wŽ
Ph 3 P5S
8
.
x
Ž . Ž
.
thiophosphinyl phenyl butan-2-one 2 48 mg, 61% as
a colourless oil which crystallised from CHCl3rpentane
as colourless crystals, m.p. 126–1278C. Anal. found: C,
72.15; H, 5.63; C22 H21OPS calcd.: C, 72.51; H, 5.81%.
1H NMR 300.13 MHz CDCl3 : d 7.77 m, 4H,
Ž
. Ž
.
Ž
.
Ž
.
Ž
.
Ar–H , 7.48 m, 7H, Ar–H , 7.30 m, 1H, Ar–H , 7.10
X
X
3
Ž
.
Ž
.
Ž
m, 1H, H-5 , 6.92 m, 1H, H-6 , 3.03 t, Js7.8 Hz,
3
.
Ž
.
Ž
2H, H-4 , 2.73 t, Js7.8 Hz, 2H, H-3 , 2.02 s, 3H,
13
.
.
Ž
. Ž
.
Ž
H-1 . C NMR 75.47 MHz CDCl3 : d 208.1 s,
2
X
2
Ž
.
Ž
Y
C-2 , 145.9 s, JPC s9.1 Hz, C-2 , 133.1 d, JPC
s
X
1
.
Ž
.
12.0 Hz, C-6 , 132.8 s, JPC s84.3 Hz, C-1 , 132.3
2
Y
Y
4
Ž
.
Ž
d, JPC s10.6 Hz, C-2 , C-6 , 132.0 d, JPC s2.1
X
1
X
.
Ž
.
Ž
Hz, C-4 , 131.9 s, JPC s85.0 Hz, C-1 , 131.7 d,
2. Experimental details
4
Y
3
X
.
Ž
.
s
JPC s1.9 Hz, C-4 , 131.6 d, JPYC s10.2 Hz, C-3 ,
3
Y
3
Ž
.
Ž
.
128.7 d, JPC s12.5 Hz, C-3 , C-5 , 125.9 d, JPC
X
.
Ž
.
Ž
Ž
Instrumental methods have been described previously
1 . Reactions were performed under an atmosphere of
12.7 Hz, C-5 , 45.2 t, C-3 , 29.8 q, C-1 , 28.6 t,
3
31
w x
.
Ž
. Ž
.
JPC s6.2 Hz, C-4 . P NMR 36.23 MHz CDCl3 : d
q
Ž
.
.
dry nitrogen but subsequent work-up was carried out
without precautions to exclude air. The orthoman-
ganated triphenylphosphine chalcogenides were pre-
42.1. GCMS: mrz 364 M
2.1.1.2. In methanol. The orthomanganated sulfide 1b
100 mg, 0.218 mmol and butenone 0.025 mL, 0.300
w x
Ž
.
Ž
pared as described elsewhere 1 . Preparative layer chro-
Ž
.
.
matography PLC was performed on 20=20 cm glass
plates coated with Merck Kieselgel 60 silica gel.
Petroleum spirits refers to a 60–808C fraction. Electro-
spray mass spectra were recorded on a Fisons VG
mmol were refluxed in methanol for 5.5 h. The residue
Ž
.
Ž .
was chromatographed PLC, CH2Cl2 to give:
Ž .
i
Ž
.
wŽ
Ph 3 P5S 18 mg, 28% ; ii 4- 2-diphenyl-
.
x
Ž . Ž
.
thiophosphinyl phenyl butan-2-one 2 43 mg, 54% .
Ž
.
Platform II instrument, using MeCNrH2O 1:1 as
mobile phase while high-resolution EI mass spectra
were recorded on a VG 70-SE mass spectrometer.
2.1.1.3. In benzene. The same reaction in benzene for
Ž .
Ž
. Ž .
Ž . Ž
wŽ
72 h gave: i Ph3P5S 25 mg, 38% ; ii 4- 2-diphen-
.
x
.
ylthiophosphinyl phenyl butan-2-one 2 10 mg, 13% .
2.1.1.4. In carbon tetrachloride. The orthomanganated
Ph3P5S 1b 111 mg, 0.241 mmol and butenone 0.028
2.1. Reactions of alkenes with orthomanganated triph-
enylphosphine chalcogenides
Ž
.
Ž
.
mL, 0.338 mmol were refluxed in carbon tetrachloride
Ž
for 24 h. The residue was chromatographed PLC,
Ž . . Ž .
.
Ž
x
wŽ
General procedure for thermally promoted coupling
reactions of alkenes with orthomanganated triph-
enylphosphine chalcogenides: The orthomanganated
CH2Cl2 to give: i Ph3P5S 20 mg, 28% ; ii 4- 2-
.
Ž . Ž
diphenylthiophosphinyl phenyl butan-2-one 2 15 mg,
.
17% .

(
)
G.J. Depree et al.rJournal of Organometallic Chemistry 155 1998 281–291
283
2.1.2. Reactions of orthomanganated triphenylphos-
phine sulfide with methyl acrylate
static CO atmosphere for 3.5 h. The residue was chro-
Ž
.
Ž .
matographed PLC, CH2Cl
to give: i Ph3P5S
Ž
.
Ž .
2w
Ž
52% ;
ii
m ethyl 3- 2-diphenylthiophos-
Ž
Ž
.
Ž
.
.
x
Ž . Ž
.
2.1.2.1. In acetonitrile. Ph2 P
CO
1b
phinyl phenyl propanoate 4 30% .
4
Ž
.
Ž
101 mg, 0.219 mmol and methyl acrylate 0.040 mL,
0.444 mmol were refluxed in acetonitrile for 3 h. The
residue was chromatographed PLC, CH Cl2 to give:
i Ph3P5S 5 mg, 8% ; ii methyl 3- 2-diphenyl-
.
Ž
Ž .
.
Ž .
Ž
.
2 w
Ž
.
x
Ž . Ž
.
thiophosphinyl phenyl propanoate 4 10 mg, 12% as
a colourless oil which crystallised from etherrpentane
as colourless crystals, m.p. 98–998C. Anal. found: C,
68.86; H, 5.78; C22 H21O2 PS calcd.: C, 68.93; H, 5.56%.
1H NMR 300.13 MHz CDCl3 : d 7.78 m, 4H,
Ž
. Ž
.
Ž
.
Ž
.
Ž
.
Ar–H , 7.48 m, 7H, Ar–H , 7.34 m, 1H, Ar–H , 7.12
m, 1H, H-5 , 6.93 m, 1H, H-6 , 3.60 s, 3H, 1-
X
X
Ž
.
Ž
.
Ž
Ž
3
3
.
Ž
.
.
.
OCH3 , 3.13 t, Js7.8 Hz, 2H, H-3 , 2.58 t, Js7.8
Hz, 2H, H-2 . 13C NMR 75.47 MHz CDCl3 : d
Ž
. Ž
.
2
X
Ž
Ž
.
Ž
173.3 s, C-1 , 145.3 s, JPC s9.5 Hz, C-2 , 133.1 d,
2
X
1
Y
.
Ž
.
s
JPC s12.0 Hz, C-6 , 132.8 s, JPYC s84.1 Hz, C-1 ,
2
Y
4
Ž
.
Ž
132.4 d, JPC s10.6 Hz, C-2 , C-6 , 132.0 d, JPC
X
1
X
.
Ž
.
Ž
2.2 Hz, C-4 , 132.1 s, JPC s85.1 Hz, C-1 , 131.7 d,
2.1.3. Reactions of orthomanganated triphenylphos-
phine sulfide with acrylonitrile
4
Y
3
X
.
Ž
.
s
JPC s2.1 Hz, C-4 , 131.3 d, JPYC s10.0 Hz, C-3 ,
3
Y
3
Ž
.
Ž
128.6 d, JPCX s12.5 Hz, C-3 , C-5 , 126.0 d, JPC
.
Ž
.
Ž
.
Ž
Ž
Ž
.
Ž
.
1b
12.4 Hz, C-5 , 51.6 q, 1-OCH3 , 35.1 t, C-2 , 29.3 t,
2.1.3.1. In acetonitrile. Ph2 P
CO
4
3
31
.
Ž
. Ž
.
Ž
.
Ž
JPC s5.9 Hz, C-3 . P NMR 36.23 MHz CDCl3 : d
101 mg, 0.220 mmol and acrylonitrile 0.020 mL,
0.304 mmol were refluxed in acetonitrile for 2 h. The
Ž
.
wŽ
.
42.0;
iii
m ethyl 2-acetyl-3- 2-diphenyl-
.
x
Ž . Ž
.
Ž
.
.
thiophosphinyl phenyl propanoate 5 54 mg, 58% as
a colourless oil which crystallised from etherrpentane
as chunky colourless crystals, m.p. 117–1198C. HRMS
residue was chromatographed PLC, CH2Cl2 to give:
Ž . Ž .
Ž
wŽ
i
Ph3 P5S
4
mg, 6% ; ii 3- 2-diphenyl-
Ž . Ž
.
x
.
thiophosphinyl phenyl propanenitrile 6 34 mg, 44%
Found: Mq, 422.1101; C24 H23O3PS calcd.: M,
as a colourless oil which crystallised from CHCl3rpen-
tane as colourless plates, m.p. 150–1518C. HRMS
found: Mq, 347.0892; C21H18 NPS calcd.: M, 347.0898.
1
Ž
. Ž
.
Ž
422.1106. H NMR 300.13 MHz CDCl3 : d 7.75 m,
.
Ž
.
Ž
.
.
4H, Ar–H , 7.45 m, 7H, Ar–H , 7.29 m, 1H, Ar–H ,
X
X
1H NMR 300.13 MHz CDCl3 : d 7.75 m, 4H,
Ž
.
Ž
Ž
Ž
. Ž
.
Ž
7.12 m, 1H, H-5 , 6.90 m, 1H, H-6 , 4.35 m, 1H,
H-2 , 3.63 s, 3H, 1-OCH3 , 3.42 m, 1H, H-3 , 3.18
X
.
Ž
.
.
Ž
.
Ž
.
Ž
.
Ž
.
Ar–H , 7.51 m, 8H, Ar–H , 7.18 m, 1H, H-5 , 6.90
13
X
3
Ž
Ž
.
Ž
.
Ž
.
Ž
m, 1H, H-3 , 2.14 s, 3H, 2-COCH3 . C NMR 75.47
. Ž
m, 1H, H-6 , 3.13 t, Js7.3 Hz, 2H, H-3 , 2.72 t,
3
13
.
Ž
.
Ž
.
.
Ž
. Ž
.
MHz CDCl3 : d 202.9 s, 2-COCH3 , 169.6 s, C-1 ,
Js7.3 Hz, 2H, H-2 . C NMR 75.47 MHz CDCl3 :
2
X
2
2
X
2
Ž
.
Ž
Ž
.
Ž
X
142.9 s, JPC s9.0 Hz, C-2 , 133.5 d, JPC s11.8
d 142.5 s, JPC s9.2 Hz, C-2 , 133.3 d, JPC s11.7
X
1
X
Y
X
1
.
Ž
.
Ž
.
Ž
Hz, C-6 , 132.5 s, JPC s84.1 Hz, C-1 or C-1 or
Hz, C-6 , 132.4 s, JPC s84.4 Hz, C-1 , 132.3 s,
Z
1
X
Y
Z
1
Y
2
JPC s84.6 Hz, C-1 , 132.3 d, JPC s10.6 Hz, C-2Y,
.
Ž
Ž
.
.
,
.
Ž
C-1 , 132.5 s, JPC s84.5 Hz, C-1 or C-1 or C-1 ,
Y
Z
X
X
Y
Z
Y
3
X
X
.
Ž
.
Ž
.
132.4–131.8 d, C-2 , C-2 , C-3 , C-4 , C-6 , C-6
C-6 , 132.2 d, JPC s10.4 Hz, C-3 , 132.0 d, C-4 ,
1
X
Y
Z
4
Y
3
Ž
.
Ž
.
Ž
132.1 s, JPC s84.2 Hz, C-1 or C-1 or C-1 , 128.8
132.0 d, JPC s2.2 Hz, C-4 , 128.8 d, JPC s12.6
3
Y
Y
Z
Z
Y
Y
3
X
Ž
Ž
Ž
.
.
Ž
.
.
d, JPC s12.6 Hz, C-3 , C-5 or C-3 , C-5 , 128.7
Hz, C-3 , C-5 , 127.0 d, JPC s12.5 Hz, C-5 , 119
3
Y
Y
Z
Z
3
s, C-1 , 29.9 t, JPC s6.1 Hz, C-3 , 18.6 t, C-2 . 31 P
.
Ž
.
Ž
Ž
.
Ž
d, JPC s12.3 Hz, C-3 , C-5 or C-3 , C-5 , 126.6
3
X
.
Ž
.
.
.
Ž
Ž
.
. Ž
.
Ž .
d, JPC s12.5 Hz, C-5 , 60 d, C-2 , 52.3 q, 1-OCH3 ,
NMR 36.23 MHz CDCl3 : d 41.8; iii 3-cyano-4-
32.2 t, JPC s5.8 Hz, C-3 , 30.2 q, 2-COCH3 . 31 P
3
Ž
.
Ž
.
.
2-diphenylthiophosphinyl phenyl -2-buten-2-amine 7 as
Ž
. Ž
NMR 36.23 MHz CDCl3 : d 41.9.
a colourless oil which crystallised from etherrpentane
as white crystals, m.p. 203–2068C. Anal. found: C,
69.73; H, 5.17; N, 6.90%; C23 H21N2 PS calcd.: C,
2.1.2.2. In methanol. The orthomanganated sulfide 1b
71.11; H, 5.45; N 7.22%. 1H NMR 400.13 MHz
Ž
.
Ž
Ž
.
101 mg, 0.219 mmol and methyl acrylate 0.028 mL,
.
Ž
.
Ž
.
Ž
.
0.311 mmol were refluxed in methanol for 3.5 h. The
residue was chromatographed PLC, CH Cl2 to give:
CDCl3 : d 7.80 m, 4H, Ar–H , 7.68 m, 1H, Ar–H ,
X
Ž
.
Ž
.
Ž
.
Ž
7.50 m, 7H, Ar–H , 7.13 m, 1H, H-5 , 6.84 m, 1H,
2 w
Ž
X
Ž .
Ž
. Ž .
.
Ž
.
Ž
.
i Ph3P5S 33 mg, 52% ; ii methyl 3- 2-diphenyl-
H-6 , 5.01 s, br, 2H, NH2 , 3.52 s, 2H, CH2 , 2.03
13
.
x
Ž . Ž
.
Ž
.
Ž
. Ž
.
thiophosphinyl phenyl propanoate 4 26 mg, 31% .
s, 3H, CH3 . C NMR 100.61 MHz CDCl3 : d
2
X
Ž
.
Ž
.
Ž
156.4 s, C-3 , 143.6 s, JPC s9.4 Hz, C-2 , 132.3 d,
2
Y
Y
4
.
Ž
2.1.2.3. In methanol under carbon monoxide. The same
reaction as in Section 2.1.2.2 was carried out under a
JPC s10.7 Hz, C-2 , C-6 , 132.0 d, JPC s2.4 Hz,
Y
X
1
Y
.
Ž
.
Ž
.
C-4 , 132.0 d, C-4 , 131.5 s, JPC s84.7 Hz, C-1 ,

(
)
284
G.J. Depree et al.rJournal of Organometallic Chemistry 155 1998 281–291
1
X
3
Ž
.
Ž
Y
Ž
131.4 s, JPC s85.2 Hz, C-1 , 130.1 d, JPC s9.9
was chromatographed PLC, 1:4 petroleum spiritrethyl
X
3
Y
.
Ž
.
.
Ž .
Ž
. Ž .
Hz, C-3 , 128.9 d, JPCX s12.6 Hz, C-3 , C-5 , 126.5
acetate to give: i Ph3P5S 12 mg, 17% ; ii a yellow
oil which consisted of a mixture of by integration of
proton methoxy singlets : 94% 1,2-di methoxycarbon-
3
Ž
.
Ž
.
Ž
.
.
Ž
d, JPC s12.4 Hz, C-5 , 125.1 s, CN , 75.0 s, C-2 ,
31
Ž
.
Ž
.
Ž
.
Ž
32.3 t, C-4 , 20.6 q, C-1 . P NMR 36.23 MHz
CDCl3 : d 42.4. ESMS: mrz 406 MqNH4 q, 389
Ž
Ž
.
.
Ž
.
.
w
Ž
.
x
yl -2- 2-diphenylthiophosphinyl phenyl ethenyl-tetra-
q
Ž
.
MqH . The compound 7 was further characterised
carbonylmanganese 8a which crystallised from
Ž
.
Ž
.
by an X-ray crystallography study see below .
CHCl3rpentane as yellow crystals 81 mg, 57% , m.p.
164–1678C. Anal. found: C, 55.92; H, 3.06;
Ž
.
2.1.3.2. In methanol. Complex 1b 101 mg, 0.219 mmol
and acrylonitrile 0.020 mL, 0.304 mmol were refluxed
in methanol for 2 h. The residue was chromatographed
PLC, CH2Cl2 to give: i Ph3P5S 31 mg, 48% ; ii
3- 2-diphenylthiophosphinyl phenyl propanenitrile
C28 H20O8 PSMn calcd.: C, 55.82; H, 3.35%. IR
y1
Ž
.
Ž
.
Ž
.
Ž .
Ž
.
Ž .
CHCl3 : y CO 2081 m , 2001 vs, br , 1959 s cm
.
1
Ž
. Ž
.
Ž
H NMR 300.13 MHz CDCl3 : d 7.85–7.26 m,
13H, Ar–H , 7.05 m, 1H, Ar–H , 3.58 s, 3H, 1-
OCH3 , 3.42 s, 3H, 4-OCH3 . C NMR 75.47 MHz
Ž
.
Ž .
Ž
. Ž .
.
Ž
.
Ž
13
w
Ž
.
x
Ž .
.
Ž
.
Ž
.
6
3
Ž
.
Ž
.
.
Ž
.
Ž
26 mg, 34% .
CDCl3 : d 215.6 s, br, CO , 212.8 s, br, JPC s6.5
Ž
.
Ž
.
Ž
Hz, CO , 211.5 s, br, CO , 210.3 s, br, CO , 191.3 s,
2
.
Ž
.
Ž
Ž
.
Ž
C-2 , 179.7 s, C-1 , 162.0 s, C-4 , 146.3 s, JPC s7.6
X
.
.
Ž
.
Hz, C-2 , 135.1 s, C-3 , 135.0 d, JPC s10.6 Hz ,
2.1.4. Attempted Li2 PdCl4-promoted coupling reactions
of alkenes with orthomanganated triphenylphosphine
sulfide
Ž
.
Ž . Ž . Ž .
133.3 d, JPC s9.4 Hz , 132.8 d , 132.5 d , 132.4 d ,
Ž .
Ž
.
Ž
132.3 d , 131.8 d, JPC s11.1 Hz , 129.0 d, JPC
s
s
s
1
.
Ž
.
Ž
12.1 Hz , 128.3 d, JPC s13.7 Hz , 127.9 s, JPC
1
.
Ž
.
Ž
84.1 Hz , 127.8 s, JPC s85.5 Hz , 127.6 d, JPC
2.1.4.1. Reaction with butenone in acetonitrile. PdCl2
77 mg, 0.435 mmol and LiCl 77 mg, 1.81 mmol
were stirred in dry acetonitrile 20 mL for 2 h to
solubilise the PdCl2 as Li2 PdCl4. Compound 1b 200
mg, 0.433 mmol and methyl vinyl ketone 0.050 mL,
0.601 mmol were added and the mixture refluxed for
17 h. Upon reaction the solution turned black with the
precipitation of palladium metal. The mixture was fil-
tered to remove metal, the filtrate passed through a
short silica column and the solvent evaporated under
reduced pressure. The residue was chromatographed
1
.
Ž
.
Ž
.
12.8 Hz , 127.0 s, JPC s86.1 Hz , 51.5 q, 4-OCH3 ,
Ž
.
Ž
Ž
.
31
Ž
.
Ž
. Ž
.
50.0 q, 1-OCH3 . P NMR 36.23 MHz CDCl3 : d
.
q
q
Ž
.
Ž
.
46.0. ESMS: mrz 620 MqNH4 , 603 MqH ;
Ž
6% of an unidentified orange crystalline solid which
.
Ž
crystallised from CHCl3rpentane as small orange
.
Ž
.
rosettes 5 mg, 3% based on a molecular mass of 716 .
1
IR CHCl3 : y CO 2027 s , 1942 s , 1918 s cmy1. H
Ž
.
Ž
.
Ž .
Ž .
Ž .
Ž
. Ž
.
Ž
NMR 300.13 MHz CDCl3 : d 7.83–7.16 m, 14H,
.
Ž
Ž
.
Ž
.
Ar–H , 4.00 s, 3H, –OCH3 , 3.80 s, 3H, –OCH3 ,
3.52 s, 3H, –OCH3 , 3.16 s, 3H, –OCH3 . ESMS:
mrz 775 MqNH4 qCH3CN , 734 MqNH4 ,
.
Ž
.
q
q
Ž
.
Ž
.
Ž
.
Ž
.
PLC, CH2Cl2 to give Ph3P5S 8 mg, 6% but no
major product.
q
Ž
.
717 MqH .
The reaction was repeated with an excess of dimethyl
acetylenedicarboxylate, but the results were not signifi-
cantly altered. Similarly a longer reaction time did not
enhance the yield of the orange compound.
2.1.4.2. Reaction with methyl Õinyl ketone in methanol.
Similarly PdCl2 39 mg, 0.220 mmol and LiCl 40 mg,
0.934 mmol were stirred in dry methanol 20 mL and
treated with 1b 101 mg, 0.219 mmol and methyl vinyl
ketone 0.025 mL, 0.300 mmol . The mixture was
stirred at ambient temperature for 60 h, by which time
t.l.c. showed the presence of the orthomanganated com-
pound and Ph3P5S. The mixture was refluxed for 3 h.
T.l.c. showed no major organic products except Ph3P5S
so the reaction was abandoned.
Ž
.
Ž
.
Ž
.
Ž
.
Ž
.
2
(
) [(
2.2.2. Reaction of h - C,S - 2-diphenylthiophos-
phinyl phenyl dicarbonylbis trimethylphosphite manga-
nese with dimethyl acetylenedicarboxylate in benzene
s u b s titu te d
CO P OMe
and dimethyl acetylenedicarboxylate 0.056 mL, 0.416
)
]
(
)
T h e
c o m p le x
P h P -
2
Ž
Ž
.
w
Ž
.
3x2
Ž
.
112 mg, 0.172 mmol
2
Ž
.
mmol were refluxed in benzene for 3 h. The residue
Ž .
Ž
.
was chromatographed PLC, CH2Cl2 to give:
i
2.2. Coupling reactions of alkynes with orthoman-
ganated triphenylphosphine sulfide
Ž
. Ž .
Ph3P5S 6 mg, 10% ; ii unreacted starting complex
. Ž
Ž
.
Ž
x
.
wŽ
11 mg, 9% ; iii E-1,2-di methoxycarbonyl -2- 2-di-
.
Ž
phenylthiophosphinyl phenyl ethenyldicarbonylbis tri-
.
Ž
. Ž
.
methylphosphite -manganese 8b 41 mg, 30% which
crystallised from CHCl3rpentane as yellow crystals,
2.2.1. Reaction of orthomanganated triphenylphosphine
sulfide with dimethyl acetylenedicarboxylate in benzene
Ž
.
Ž
.
.
Ž .
Ž .
m.p. 179–1828C. IR CHCl3 : y CO 1950 s , 1870 s .
1
Ž
Ž
. Ž . Ž
.
Ž
. Ž
Ž
Ž
Ph2 P
CO 1b 109 mg, 0.237 mmol
H NMR 300.13 MHz CDCl3 : d 7.70–7.10 m, 4H,
4
Ž
.
Ž
Ž
. .
and dimethyl acetylenedicarboxylate 0.044 mL, 0.358
mmol were refluxed in benzene for 3.5 h. The residue
Ar–H , 3.64 m, 18H, P OCH3 , 3.42 s, 3H,
–COOCH3 , 3.19 s, 3H, –COOCH3 . P NMR 36.23
3
31
.
.
Ž
.
Ž

(
)
G.J. Depree et al.rJournal of Organometallic Chemistry 155 1998 281–291
285
. Ž
.
MHz CDCl3 : d 176.5, 175.7, 42.9. ESMS: mrz 812
6. with 2-methyl-1-buten-3-yne in refluxing aceto-
nitrile.
q
q
Ž
.
Ž
.
MqNH4 , 795 MqH .
2.4. Sulfur dioxide insertion reactions of orthoman-
ganated triphenylphosphine chalcogenides
2.2.3. Reaction of orthomanganated triphenylphosphine
sulfide with methyl propiolate in benzene
Ž
.
Methyl propiolate 0.030 mL, 0.337 mmol and 1b
102 mg, 0.222 mmol were refluxed in benzene for 3.5
Ž
.
Ž
.
h. The residue was chromatographed PLC, CH2Cl2 to
Ž . Ž . Ž .
Ph3P5S 7 mg, 11% ; ii Z-1-methoxy-
give:
carbonyl-2- 2-diphenylthiophosphinyl phenyl -ethenyl-
. Ž
i
w
Ž
.
x
Ž
.
tetracarbonylmanganese 8c 49 mg, 41% as a yellow
Ž
.
Ž
.
Ž .
Ž
.
Ž
oil. IR CHCl3 : y CO 2077 m , 1997 vs, br , 1989 vs,
br , 1947 s cm . H NMR 300.13 MHz CDCl3 : d
1
y1
.
Ž .
Ž
. Ž
.
Ž
.
Ž
.
Ž
7.72–7.48 m, 12H, Ar–H , 7.37 s, 1H, H-3 , 7.22 m,
X
X
.
Ž
.
Ž
.
1H, H-5 , 6.99 m, 1H, H-6 , 3.45 s, 3H, 1-OCH3 .
13
Ž
. Ž
.
Ž
.
C NMR 75.47 MHz CDCl3 : d 217.3 s, br, C[O ,
213.7 s, br, C[O , 212.7 s, br, 2=C[O , 179.1 s,
Ž
.
Ž
.
Ž
X
2
.
Ž
.
Ž
Ž
.
C-2 , 165.6 s, C-1 , 147.1 s, JPC s8.1 Hz, C-2 ,
X
X
Y
Y
Ž
.
142.5 d, C-3 , 132.7–131.6 d, C-4 , C-6 , C-2 , C-4 ,
Y
3
Y
Y
.
Ž
.
Ž
C-6 , 128.9 d, JPC s12.2 Hz, C-3 , C-5 , 128.8 d,
X
1
Y
3
.
Ž
.
Ž
C-3 , 128.3 s, JPC s84.8 Hz, C-1 , 126.7 d, JPC
s
X
1
X
.
Ž
Ž
.
Ž
12.5 Hz, C-5 , 125.8 s, JPC s85.0 Hz, C-1 , 50.7 q,
31
2.4.1. Reaction of orthomanganated triphenylphosphine
sulfide with sulfur dioxide
.
. Ž
.
1-OCH3 . P NMR 36.23 MHz CDCl3 : d 45.2.
ESMS: mrz 562 MqNH4 q, 545 MqH q, 517
Ž
.
Ž
.
q
Ž
.
.
Ž .
x
wŽ
M q H–CO
;
iii methyl E-3- 2-diphenyl-
Ž
Ž
.
4
2.4.1.1. Thermally induced. Ph2 P
CO 1b
Ž
. Ž
.
thiophosphinyl phenyl prop-2-enoate 10 11 mg, 13%
as a colourless oil. HRMS found: Mq, 378.0843;
Ž
.
300 mg, 0.651 mmol was placed in an ampoule and
1
degassed. Liquid SO2 , which had been degassed by two
cycles of freeze–pump–thawing was condensed into the
ampoule using standard vacuum line techniques. The
ampoule was sealed and placed in a Carius tube main-
tained at 528C for 18 h. The ampoule was opened and,
after the excess SO2 had evaporated, the residue was
extracted with dichloromethane and filtered. An infrared
Ž
C22 H19O2 PS calcd.: M, 378.0843. H NMR 300.13
3
. Ž
.
Ž
.
MHz CDCl3 : d 8.25 d, Js15.7 Hz, 1H, H-3 , 7.84
Ž
.
Ž
.
3
Ž
m, 4H, Ar–H , 7.50 m, 8H, Ar–H , 7.30 m, 1H,
X
X
.
Ž
.
Ž
H-5 , 7.16 m, 1H, H-6 , 6.08 d, Js15.7 Hz, 1H,
13
.
Ž
.
Ž
.
H-2 , 3.64 s, 3H, 1-OCH3 . C NMR 75.47 MHz
3
Ž
.
Ž
.
Ž
X
CDCl3 : d 166.4 s, C-1 , 143.2 d, JPC s7.0 Hz,
2
1
.
Ž
.
Ž
C-3 , 138.4 s, JPC s7.4 Hz, C-2 , 133.4 s, JPC
s
X
2
X
spectrum showed complete conversion to the SO2 inser-
.
Ž
.
82.9 Hz, C-1 , 133.1 d, JPC s10.9 Hz, C-6 , 132.5
2
2
Y
Y
1
Ž
.
w
Ž
.
tion product h - S,S - 2-diphenylthiophosphinyl phen-
Ž
.
Ž
d, JPC s10.6 Hz, C-2 , C-6 , 132.1 s, JPC s84.8
Y
4
X
x
Ž
.
ylsulfonyl tetracarbonylmanganese 11b by the absence
Ž .
.
Ž
.
Ž
Hz, C-1 , 132.0 d, JPC s2.0 Hz, C-4 , 131.9 d,
4
Y
3
X
Ž
.
Ž
.
of the peaks at 2072 m , 1993 vs, br , 1978 vs, br ,
.
Ž
.
.
JPC s2.1 Hz, C-4 , 129.1 d, JPC s12.3 Hz, C-5 ,
y1
3
Y
Y
X
Ž .
1933 s cm
and the appearance of peaks at higher
Ž
Ž
. Ž
.
Ž
128.6 d, JPC s12.5 Hz, C-3 , C-5 , 128.6 d, C-3 ,
31
frequency. Vapour diffusion of pentane into a saturated
.
.
.
.
Ž
.
Ž
.
120.0 d, C-2 , 51.6 q, 1-OCH3 . P NMR 36.23
q
dichloromethane solution of 11b gave small yellow
Ž
MHz CDCl3 : d 41.4. GCMS: mrz 378 M , 319
q
Ž
.
crystals 304 mg, 89% , m.p. 119–1218C. Anal. found:
Ž
M–COOCH3
C, 49.85; H, 2.61; C22 H14O6S2 MnP calcd.: C, 50.39; H
Ž
.
Ž
.
Ž .
Ž .
Ž .
2.69%. IR CHCl3 : y CO 2101 m , 2030 s , 2014 s ,
1
y1
Ž .
Ž
. Ž
.
1986 s cm
.
H NMR 300.13 MHz CDCl3 : d
2.3. Unsuccessful coupling reactions with alkynes
Ž
.
Ž
.
Ž
8.40 m, 1H, H-6 , 7.78 m, 1H, H-5 , 7.63–7.48 m,
10H, Ar–H , 7.39 m, 1H, H-4 , 6.90 m, 1H, H-3 . 13C
Ž . Ž . Ž .
NMR 75.47 MHz CDCl3 : d 212.6 s, br, C[O ,
.
Ž
.
Ž
.
No new species were isolated from the following
Ž
Ž
.
Ž . Ž . Ž
212.1 s, br, C[O , 208.1 s, br, 2=C[O , 157.2 s,
2
reactions of Ph2 P
CO :
4
. Ž . Ž
JPC s8.2 Hz, C-1 , 134.0 d, C-5 , 133.9 d, C-3 ,
X X
2
.
.
1. with Ph2C2 in refluxing benzene, petroleum spirit or
acetonitrile;
2. with 3-butyn-1-ol in refluxing benzene;
3. with 2-methyl-3-butyn-2-ol in refluxing benzene
4. with C2 H2 in refluxing petroleum spirit;
5. with trimethylsilylacetylene in refluxing benzene;
X
Ž
.
Ž
133.3 d, C-4 , 133.0 d, JPC s10.7 Hz, C-2 , C-6 ,
3
3
Ž . Ž
129.7 d, JPCX s12.1 Hz, C-4 , 129.0 d, JPC s13.5
X X
1
.
Ž
.
Hz, C-3 , C-5 , 127.9 s, JPC s90.1 Hz, C-1 , 126.1
3
1
Ž
.
Ž
.
d, JPC s8.1 Hz, C-6 , 124.2 s, JPC s80.6 Hz, C-2 .
31
Ž
. Ž
.
P NMR 36.23 MHz CDCl3 : d 34.6. ESMS: 547

(
)
286
G.J. Depree et al.rJournal of Organometallic Chemistry 155 1998 281–291
MqNa q, 542 MqNH4 q, 538 MqH–COq
Ž
.
Ž
.
Ž
2.5. X-ray crystal structure determinations
q
q
q
.
Ž
.
Ž
.
CH3CN , 525 MqH , 497 MqH–CO .
(
)
)
2.5.1. 3-cyano-4- 2-diphenylthiophosphinyl phenyl -2-
( )
2.4.1.2. Photochemically induced. Orthomanganated
Ph3P5S 107 mg, 0.232 mmol was sealed in an am-
buten-2-amine 7
Ž
.
White crystals were obtained from etherrpentane.
The unit cell dimensions and intensity data were ob-
tained on a Siemens SMART CCD diffractometer. The
data collection nominally covered over a hemisphere of
reciprocal space, by a combination of three sets of
exposures; each set had a different f angle for the
crystal and each exposure covered 0.38 in v. The
crystal to detector distance was 5.0 cm. The data sets
were corrected empirically for absorption using SAD-
ABS.
Ž
.
poule with SO2 ;10 mL and placed under a UV
lamp for 18 h at ambient temperature. An infrared
spectrum of the residue showed complete conversion to
Ž
.
the SO2 insertion product 11b 106 mg, 87% .
2.4.2. Reaction of orthomanganated triphenylphosphine
selenide with sulfur dioxide
Ž
Ž
.
CO
4
Ž
. Ž
Similarly, Ph2 P
1c 252 mg,
.
Ž
.
0.496 mmol was treated with SO2 ;10 mL and left
to react for 18 h at 528C. An infrared spectrum showed
The structure was solved by direct methods and
developed routinely. In the final cycles of least-squares
refinement based on F2 against all data SHELXL-96
Ž
the complete conversion to the SO2 insertion product,
2
Ž
.
w
Ž
.
w
x.
h - S,Se - 2-diphenylselenophosphinyl phen-
7a,7b,7c , all non-hydrogen atoms were treated
x
Ž
.
ylsulfonyl tetracarbonylmanganese 11c . Vapour diffu-
sion of pentane into a saturated dichloromethane solu-
tion gave small yellow crystals 238 mg, 84% , m.p.
133–1358C. Anal. found: C, 45.96; H, 2.19%;
C22 H14O6SMnPSe calcd.: C, 46.25; H 2.47%. IR
anisotropically and hydrogen atoms were included in
their calculated positions, except for the NH2 hydrogen
atoms of the two independent molecules which were
located as the four highest residual peaks in a penulti-
mate difference map, and were included in the final
refinement with fixed Uiso values, but with uncon-
strained coordinates.
Ž
.
Ž
.
Ž
.
Ž .
Ž .
Ž .
Ž .
CHCl31 : y CO 2096 m , 2026 s , 2009 s , 1982 s
cmy1. H NMR 300.13 MHz CDCl3 : d 8.40 m,
. Ž
Ž
.
Ž
.
Ž
.
Ž
1H, H-6 , 7.78 m, 1H, H-5 , 7.62–7.52 m, 10H,
Crystal data: C23 H21N2 PS, Mr 388.45, triclinic,
Ar–H , 7.39 m, 1H, H-4 , 6.90 m, 1H, H-3 . 13C
.
Ž
.
Ž
.
Ž .
Ž .
Ž .
space group P1, as12.3771 3 , bs13.4731 3 , cs
2
˚
Ž
. Ž
.
Ž
Ž .
Ž .
NMR 75.47 MHz CDCl3 : d 157.8 s, JPC s9.1 Hz,
14.4548 3 A, as96.924 1 , bs107.937 1 , gs
2
109.478 1 8, Us2094.01 7 A , Dcalc s1.232 g cmy3
,
3
˚
.
Ž
.
Ž
.
Ž
Ž .
Ž .
C-1 , 134.0 d, C-5 , 133.5 d, C-3 , 133.4 d, JPC
s
X
X
4
X
Zs4, F 000 816, m Mo K a s0.24 mmy1. Crystal
size 0.37=0.32=0.21 mm3. A total of 20291 reflec-
tions were collected at 203 K in the range 1.6-u-
.
Ž
.
Ž
.
Ž
.
10.8 Hz, C-2 , C-6 , 133.2 d, JPC s2.6 Hz, C-4 ,
3
3
Ž
.
Ž
129.6 d, JPCX s11.4 Hz, C-4 , 129.0 d, JPC s13.6
X
1
X
.
Ž
.
Hz, C-3 , C-5 , 126.9 s, JPC s82.0 Hz, C-1 , 126.9
3
1
Ž
.
Ž
.
Ž
d, JPC s8.3 Hz, C-6 , 123.6 s, JPC s73.4 Hz, C-2 .
28.28, corresponding to 9214 unique data Rint s0.027,
31
Ž
.
. Ž
.
P NMR 36.23 MHz CDCl3 : d 15.6. ESMS: 590
Tmax, min 0.9623, 0.7857.
q
q
q
Ž
Ž
.
Ž
.
w
MqNH4 , 573 MqH , 545 MqH–CO . This
The refinement converged with R1 s0.0442 for
Ž .
x
compound was further characterised by an X-ray crystal
7100 data with I)2s I , R1 s0.0667, wR2 0.1096,
Ž
.
Ž
.
structure determination see below .
GoF 1.043 all data . The largest features in a final
difference map were q0.279ry0.330 e Ay3. Coordi-
˚
nates are listed in Table 1 and the structure of one of the
independent molecules is illustrated in Fig. 1, with
selected bond parameters given in Table 2.
2.4.3. Reaction of orthomanganated triphenylphosphine
oxide with sulfur dioxide
Ž
Ž
. Ž . Ž .
Ph2 P
CO 1a 273 mg, 0.614 mmol
4
Ž
.
(
)
[(
was treated with SO2 ;10 mL and left to react for 18
h at 528C. An orange oil which failed to crystallise was
2.5.2. 1,2-di methoxycarbonyl -2- 2-diphenyl-
thiophosphinyl phenyl ethenyl-tetracarbonylmanganese
2-diphenylselenophosphinyl phenyl-sulfo-
nyl tetracarbonyl-manganese 11c
For both of these compounds only poor quality deter-
minations were possible. For 11c only mediocre quality
crystals were obtained by slow diffusion of pentane into
a concentrated solution in CHCl3, whereas for 8a the
crystals appeared to be of reasonable quality but the
refinement gave poor R indices, possibly because of
twinning problems. Both structure analyses confirmed
the atom connectivity and the gross features of the
molecules concerned, but only the crystal data is pre-
)
]
(
)
]
[(
)
obtained, and was tentatively assigned as consisting of:
8a and
2
Ž .
Ž
.
w
Ž
.
x
(
)
i
h - S,O - 2-diphenylphosphinyl phenylsulfonyl te-
Ž
.
Ž
tracarbonyl-manganese, 11a ESMS: 522 MqH–CO
q
q
q
.
Ž
.
Ž
.
qCH3CN , 509 MqH , 481 MqH–CO and
Ž .
Ž
ii an unidentified product with ESMS: 800 MqH–
q
q
q
.
Ž
.
Ž
.
COqCH3CN , 787 MqH , 759 MqH–CO .
)
Ž
.
Ž
Ž .
.
Ž .)
Ž .
Combined IR CHCl3 : y CO 2109 m , 2044 vs
,
.
)
y1
Ž
.
Ž .)
2036 vs , 2010 s 1978 s , 1959 vs , 1930 vs cm
Ž
.
Ž .
31
)
Ž
. Ž
.
Combined P NMR 36.23 MHz CDCl3 : d 44.4 ,
41.9. The peaks indicated by an asterisk are tentatively
assigned to 11a.

(
)
G.J. Depree et al.rJournal of Organometallic Chemistry 155 1998 281–291
287
Table 1
Atomic coordinates and equivalent isotropic displacement parameters
for 7
Ž .
U eq
x
y
z
Ž .
S 1
Ž .
0.2860 1
0.1288 1
Ž .
0.4914 1
0.4496 1
Ž .
0.7236 1
0.7437 1
Ž .
0.034 1
P 1
Ž .
Ž .
Ž .
Ž .
Ž .
0.049 1
Ž
.
.
.
.
.
Ž .
Ž .
Ž .
Ž .
0.035 1
C 11
0.3314 2
0.7468 1
0.7771 1
Ž
Ž .
Ž .
Ž .
Ž .
0.035 1
C 12
0.2938 2
0.8262 1
0.8303 2
Ž
Ž .
Ž .
Ž .
Ž .
0.039 1
C 13
0.3646 2
0.9393 2
0.8505 2
Ž
Ž .
Ž .
Ž .
Ž .
0.046 1
C 14
0.1934 2
0.7953 2
0.8567 2
Ž
Ž .
Ž .
Ž .
Ž .
0.066 1
C 15
0.1548 3
0.8753 2
0.9061 2
Ž
.
Ž .
Ž .
Ž .
Ž .
0.056 1
N 11
0.4224 2
1.0303 1
0.8658 2
Ž
.
Ž .
Ž .
Ž .
Ž .
0.069 1
N 12
0.1213 2
0.6903 2
0.8408 2
Ž
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
Ž .
Ž .
Ž .
Ž .
0.030 1
C 111
0.4127 2
0.5992 1
0.8271 1
Ž
Ž .
Ž .
Ž .
Ž .
0.035 1
C 112
0.5008 2
0.5711 2
0.8936 1
Ž
Ž .
Ž .
Ž .
Ž .
0.041 1
C 113
0.5961 2
0.6477 2
0.9763 2
Ž
Ž .
Ž .
Ž .
Ž .
0.043 1
C 114
0.6048 2
0.7537 2
0.9938 2
Ž
Ž .
Ž .
Ž .
Ž .
0.038 1
C 115
0.5181 2
0.7825 2
0.9290 2
Ž
Ž .
Ž .
Ž .
Ž .
0.031 1
C 116
0.4207 2
0.7073 1
0.8454 1
Ž
Ž .
Ž .
Ž .
Ž .
0.041 1
C 121
0.3325 2
0.3771 2
0.7105 2
Ž
Ž .
Ž .
Ž .
Ž .
0.054 1
C 122
0.2712 2
0.2833 2
0.7345 2
Fig. 1. The structure of one of the independent molecules of the
enamine 7. The labelling scheme for each molecule is generated by
Ž
Ž .
Ž .
Ž .
Ž .
0.073 1
C 123
0.3062 3
0.1950 2
0.7253 2
Ž
Ž .
Ž .
Ž .
Ž .
0.078 1
Ž .
Ž .
C 124
0.4007 3
0.2009 2
0.6941 2
adding 1 or 2 appropriately; for example N 1 becomes N 11 for
Ž
Ž .
Ž .
Ž .
Ž .
0.079 1
Ž
.
C 125
0.4631 3
0.2939 3
0.6706 2
molecule 1 and N 21 for molecule 2.
Ž
Ž .
Ž .
Ž .
Ž .
0.063 1
C 126
0.4283 3
0.3823 2
0.6778 2
Ž
Ž .
Ž .
Ž .
Ž .
0.037 1
C 131
0.2840 2
0.5416 2
0.6123 1
2
Ž
Ž
w x.
SHELXS-86 7b and the refinement was based on F
Ž
Ž .
Ž .
Ž .
Ž .
0.050 1
C 132
0.3931 2
0.6120 2
0.6074 2
w
x.
SHELXL-93 7b .
Crystal data for 8a: C28 H20 MnO8 PS.CHCl3, Mr s
Ž .
Ž
Ž .
Ž .
Ž .
Ž .
0.068 1
C 133
0.3910 3
0.6551 2
0.5252 2
Ž
Ž .
Ž .
Ž .
Ž .
C 134
0.2805 3
0.6280 3
0.4476 2
0.075 1
Ž .
0.070 1
Ž
Ž .
Ž .
Ž .
C 135
0.1727 3
0.5579 3
0.4503 2
721.78, triclinic, space group P1, as10.810 3 , bs
Ž
Ž .
Ž .
Ž .
Ž .
C 136
0.1731 2
Ž .
0.5142 2
Ž .
0.5325 2
Ž .
0.050 1
Ž .
0.032 1
˚
Ž .
Ž .
Ž .
Ž .
11.831 4 , c s 14.347 7 A, a s 67.67 4 , b s
Ž .
P 2
0.7591 1
1.0069 1
0.6933 1
3
˚
Ž .
91.19 1 , gs87.088, Vs1695 1 A , Dcalc s1.414 g
Ž .
Ž .
Ž .
Ž .
Ž .
S 2
0.5927 1
0.9883 1
0.6879 1
0.045 1
Ž .
0.032 1
cmy3, for Zs2; 4379 unique reflections, 48-2u-558,
Ž
.
.
.
.
.
.
.
Ž .
Ž .
Ž .
C 21
0.8257 2
1.2610 1
0.7751 1
Ž
Ž .
Ž .
Ž .
Ž .
Ž .
3306 with I)2s I . Best refinement gave R1 s0.1234
C 22
0.7938 2
Ž .
1.3388 1
Ž .
0.8367 1
Ž .
0.032 1
Ž .
0.037 1
Ž
C 23
0.8472 2
1.4514 2
0.8431 1
Ž
.
Ž
2s data ; R1 s0.1391, wR2 s0.3588, GoF 1.035 all
Ž
Ž .
Ž .
Ž .
Ž .
C 24
0.7149 2
1.3056 2
0.8857 2
0.037 1
Ž .
0.050 1
.
data . Attempted refinement in P1 was equally unsuc-
cessful. The structure is illustrated in Fig. 2.
Ž
Ž .
Ž .
Ž .
C 25
0.6857 2
1.3836 2
0.9473 2
Ž
Ž .
Ž .
Ž .
Ž .
N 21
0.8890 2
Ž .
1.5425 1
Ž .
0.8465 2
Ž .
0.055 1
Ž .
0.048 1
Crystal data for 11c: C22 H14 MnO6 PSSe, Mr s
Ž
N 22
0.6600 2
1.1999 1
0.8831 2
Ž
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
Ž .
Ž .
Ž .
Ž .
Ž .
C 211
0.8845 2
1.0979 1
0.8083 1
0.030 1
Ž .
0.036 1
571.26, monoclinic, space group P21rc, as13.09 3 ,
Ž
Ž .
Ž .
Ž .
C 212
0.9657 2
1.0583 2
0.8680 1
Ž
Ž .
Ž .
Ž .
Ž .
C 213
1.0630 2
Ž .
1.1252 2
Ž .
0.9550 2
Ž .
0.039 1
Ž .
0.041 1
Table 2
Ž
C 214
1.0809 2
1.2332 2
0.9839 2
Selected bond parameters for the enamine compound 7
Ž
Ž .
Ž .
Ž .
Ž .
0.036 1
C 215
1.0020 2
1.2733 2
0.9258 1
Ž
Ž .
Ž .
Ž .
Ž .
0.030 1
˚
Ž .
C 216
0.9037 2
1.2083 1
0.8373 1
Bond A
Molecule 1
Ž .
Molecule 2
Ž .
1.9649 7
Ž
Ž .
Ž .
Ž .
Ž .
0.035 1
C 221
.7995 2
1.0611 1
0.5940 1
P–S
Ž .
1.9604 7
Ž
Ž .
Ž .
Ž .
Ž .
0.048 1
C 222
0.7086 2
1.0550 2
0.5063 2
Ž
Ž .
Ž .
C 1 –C 16
1.525 2
1.524 2
Ž .
1.366 2
Ž
Ž .
Ž .
Ž .
Ž .
0.061 1
C 223
0.7407 2
1.0957 2
0.4307 2
Ž . Ž .
Ž .
C 2 –C 4
1.359 2
Ž
Ž .
Ž .
Ž .
Ž .
0.063 1
C 224
0.8617 2
1.1432 2
0.4415 2
Ž . Ž .
Ž .
Ž .
C 4 –N 2
1.343 2
Ž .
1.347 2
Ž .
1.521 2
Ž
Ž .
Ž .
Ž .
Ž .
0.065 1
C 225
0.9534 2
1.1504 2
0.5289 2
Ž . Ž .
C 1 –C 2
1.518 2
Ž
Ž .
Ž .
Ž .
Ž .
0.052 1
C 226
0.9229 2
1.1096 2
0.6051 2
Ž . Ž .
Ž .
Ž .
1.417 2
C 2 –C 3
1.421 2
Ž
Ž .
Ž .
Ž .
Ž .
0.038 1
C 231
0.7720 2
0.8757 2
0.6837 2
Ž . Ž .
Ž .
Ž .
C 3 –N 1
1.148 2
Ž .
1.150 2
Ž
Ž .
Ž .
Ž .
Ž .
C 232
0.7286 2
0.8094 2
0.7422 2
0.044 1
Ž .
0.054 1
Ž . Ž .
Ž .
C 4 –C 5
1.506 2
Molecule 1
Ž .
1.502 2
Molecule 2
Ž .
Ž
Ž .
Ž .
Ž .
C 233
0.7355 2
0.7084 2
0.7364 2
Ž
Ž .
Ž .
Ž .
Ž .
0.070 1
C 234
0.7824 3
0.6719 2
0.6710 2
Ž .
Angle 8
Ž
Ž .
Ž .
Ž .
Ž .
0.087 1
C 235
0.8225 3
0.7355 2
0.6113 3
Ž
.
.
S–P–C 11
112.94 7
114.91 7
Ž
Ž .
0.8187 3
Ž .
0.8381 2
Ž .
0.6179 2
Ž .
0.063 1
C 236
Ž
Ž .
Ž .
S–P–C 31
114.26 7
109.30 7
Ž . Ž . Ž .
Ž .
118.4 2
Ž .
118.7 2
C 1 –C 2 –C 3
Ž . Ž . Ž .
Ž .
Ž .
C 2 –C 3 –N 1
179.1 2
178.7 2
Ž .
122.6 2
Ž . Ž . Ž .
Ž .
C 2 –C 4 –C 5
122.9 2
sented here since the detailed bond parameters cannot
be taken as being reliable. Intensity data was obtained
on a Nicolet XRD P3 four-circle diffractometer with
Ž
.
Ž .
Ž .
114.72 7
S–P–C 21
Ž . Ž .
111.68 7
Ž
.
Ž .
Ž .
114.2 2
C 16 –C 1 –C 2
115.6 2
Ž . Ž . Ž .
Ž .
Ž .
C 1 –C 2 –C 4
123.6 2
Ž .
123.3 2
˚
Ž
.
monochromated Mo K a X-rays l 0.7107 A at 130 K.
Ž . Ž . Ž .
Ž .
C 2 –C 4 –N 2
122.1 2
121.7 2
The structures were solved by direct methods

(
)
288
G.J. Depree et al.rJournal of Organometallic Chemistry 155 1998 281–291
Fig. 3. The structure of 11c, from insertion of SO2 into the Mn–C
bond of
.
butanone group has substituted for Mn at the ortho
position of one of the phenyl rings of Ph3P5S. The
same reaction in MeOH gave essentially the same re-
sult, but in the non-polar solvents CCl4 or C6 H6 much
lower yields of 2 were found. In all of these systems the
only other significant product was Ph3P5S formed by
demetallation of 1b. Based on suggested mechanisms in
Ž
.
2
Fig. 2. The structure of 8a, from insertion of C2 COOMe into the
Mn–C bond of
.
˚
Ž
˚
.
.
Ž
.
Ž .
bs9.163 13 , cs18.36 12 A, bs94.2 3 8, Vs
2196 16 A , Dcalc s1.728 g cmy3, Zs4; 2024 unique
3
Ž
Ž .
reflections, 48-2u-458, 1106 with I)2s I . Best
w
x
Ž
.
related coupling reactions 3a,3b,3c,3d,3e,3f,3g,3h , the
formation of 2 presumably involves insertion of the
alkene into the Mn–C bond of 1b, followed by demetal-
lation of the intermediate species 3a. The origin of the
proton involved in such demetallations has been investi-
refinement gave R1 s0.1003 2s data , wR2 s0.2987,
Ž
.
GoFs1.063 all data . The structure is illustrated in
Fig. 3.
w
x
gated by Cambie et al. 3d . There was no sign of the
unsaturated butenone compound that would result from
b-elimination from 3a but this process is perhaps pre-
cluded by the conformational restrictions imposed by
the chelate ring.
3. Results and Discussion
(
(
)
( )
3.1. Reactions of Ph2 P
alkenes.
CO 4 1b with
Ž
When 1b is refluxed in MeCN with butenone methyl
The corresponding reaction of 1b with methyl
Ž .
propenoate methyl acrylate gave only 12% of the
.
vinyl ketone for 2 h, the major product is 2, in which a
Scheme 1.

(
)
G.J. Depree et al.rJournal of Organometallic Chemistry 155 1998 281–291
289
analogous coupled product 4 in MeCN, with the major
product being 5. This second species is envisaged as
forming from a double insertion sequence. Initial inser-
tion of the alkene would give 3b, which then undergoes
insertion of MeCN into the new Mn–C bond. Protio-de-
metallation generates the imine of 5 which would be
hydrolysed to the final product 5 on work-up. Such
products have been previously observed in similar cou-
is the lack of insertion of CO by 3b readily explained.
These complicating secondary reactions can be avoided
by using MeOH instead of MeCN as solvent, although
demetallation of the starting material to produce
Ph3P5S is a more significant competing process in
MeOH.
Coupling reactions between orthomanganated aryl
Ž .
ketones and alkenes are promoted by Pd II
w x
w
x
pling reactions of orthomanganated aryl ketones 8 , and
3a,3b,3c,3d,3e,3f,3g,3h . The reaction of 1b with
a similar process is encountered in the reaction with
acrylonitrile discussed below. The sequence of insertion
is specific; there was no indication of MeCN insertion
into the Mn–Caryl bond of 1b, only into the Mn–CŽsp3.
bond subsequent to alkene insertion. As expected, no 5
was formed when the reaction was carried out in MeOH,
only 4 was isolated in 31% yield. When the reaction
was performed in MeOH under an atmosphere of CO,
the yield of 4 was unchanged and no product arising
from a CO insertion was identified.
butenone was therefore examined in MeCN and in
MeOH with Li2 PdCl4 present. However no tractable
products were found.
(
(
)
( )
3.2. Reactions of Ph2 P
alkynes
CO 4 1b with
Ž
.
Ž
.
DMAD was re-
When the alkyne C2 COOMe
2
acted with 1b under reflux in benzene, the major prod-
uct was that expected on insertion, namely the seven-
membered metallocycle 8a. This was unambiguously
identified by X-ray methods, Fig. 2, though the determi-
nation was of rather poor quality. Nevertheless, overall
features are clear, showing that the seven-membered
metallocyclic ring is in a strongly-puckered boat config-
uration similar to that in the analogous product from
With acrylonitrile in MeCN, 1b gave the expected
Ž
.
coupled product 6 in 44% yield 34% in MeOH , and
also gave a second species which ESMS showed to
have a mass of 41 amu greater than that of 6, indicating
the inclusion of a molecule of MeCN. An unambiguous
characterisation was not possible on the spectroscopic
evidence so an X-ray crystal structure determination
was carried out which showed that this second product
Ž
.
w
x
orthomanganated P OPh 5a,5b .
3
A minor product from the 1brDMAD reaction corre-
sponded to the addition of two moles of DMAD to, and
the loss of one mole of CO from, 1b. This was indicated
by the ES mass spectrum, by the NMR spectrum which
showed four inequivalent COOMe groups, and by the
Ž
.
is the cyano-enamine 7 Fig. 1 . A possible route to this
species is outlined in Scheme 1. The first step will be
the insertion of the C5C bond of acrylonitrile into the
Mn–C bond to give the intermediate I, which then
undergoes insertion of MeCN into the new Mn–C bond,
giving intermediate II. Protio-demetallation would then
give the primary imine III, which generates the final
amine product 7 with a 1,3-H migration driven by the
shift of the double bond into conjugation with the cyano
group. Enamines are usually the less stable form in
enamine-imine tautomerism, but the cyano groups are
Ž
.
characteristic Mn CO -group pattern in the carbonyl-
3
stretching region of the infrared spectrum. It appears
that there has been a double insertion of DMAD to give
a nine-membered metallocyclic ring which twists to
allow one of the C5C bonds to displace a CO ligand
from the manganese, as in 9. Analogous species arising
from double alkyne insertion are known for Pd
w x
known to alter the stability balance 9 .
w
x
10a,10b,10c , and a related compound was tentatively
identified from the reaction of DMAD with orthoman-
There are two crystallographically independent
molecules of 7 in the unit cell, but these do not differ in
other than conformation—the major difference is in the
dihedral angle between the plane of the
Ž
.
w
x
ganated P OPh 5a,5b . The spectroscopic properties
3
fit this assignment, but unfortunately no suitable crys-
tals could be obtained for confirmation by X-ray meth-
ods. It is clear that the route to this minor product is not
just a step-wise process, since longer reaction times
with excess DMAD did not enhance the yield.
In an attempt to obtain an example of type 9 which
would give X-ray quality crystals the reaction was
carried between the substituted complex Ph2 P-
Ž
. Ž
.
–CH2C CN C Me NH2 group and the plane of the ring
it is attached to, 728 and 888 respectively for molecule 1
and 2. The structure confirms the expected trans ar-
rangement of the CN and NH2 groups about the double
bond. In each molecule the NH2 group is orientated so
that one N–H is directed towards the S atom, indicating
at least a weak H-bond.
Ž
Ž
.
w
Ž
.3x2
For all of these reactions the manganese is displaced
during the reaction, but the first-formed species follow-
ing insertion, 3, are obviously long-lived enough to
undergo subsequent insertion of MeCN in some cases.
However it is not obvious why the butenone intermedi-
ate 3a did not add MeCN to any significant extent, nor
CO P OMe and DMAD. This gave
2
the mono-insertion product 8b, but no sign of the
corresponding di-insertion compound.
With 1b and methyl propiolate a moderate yield of
the mono-inserted product 8c was obtained, although
some demetallation occurred to produce significant

(
)
290
G.J. Depree et al.rJournal of Organometallic Chemistry 155 1998 281–291
Ž
amounts of the ortho-substituted compound 10. As is
usual in these reactions, the insertion of the unsymmet-
rical alkyne occurs regiospecifically, with the bulky
substituent adjacent to the manganese atom
aryl-alkanes rather than the aryl-alkenes or cyclised
.
species found for the ketone derivatives. Only a limited
range of alkynes react, and the first-formed insertion
product is isolable in contrast to the ketone species
where subsequent reactions ensue. In this instance there
is a closer parallel with the reactions of orthometallated
triphenylphosphite. The SO2 insertion reaction proceeds
efficiently to give stable species.
The chemistry reported here therefore provides an
interesting comparison with earlier systems. The reac-
tions allow specific addition of a variety of groups in
the ortho position of one aryl ring of the Ph3P5X
ligands, providing compounds that would be difficult to
prepare by other routes. They may therefore find appli-
cation in the synthesis of novel ligands
w
x
3a,3b,3c,3d,3e,3f,3g,3h,11 .
Only for DMAD and methyl propiolate were inser-
tion reactions observed. No new species could be iso-
Ž
lated from reactions of a range of other alkynes see
Section 2 with 1b under different conditions.
.
(
( ) ( )
CO 4 1 with SO2 .
3.3. Reactions of Ph2 P
Another reaction which is facile for orthomanganated
w x
compounds is SO2 insertion 6 . When 1b and liquid
SO2 were reacted either thermally at 528C, or photo-
chemically, essentially quantitative yields of the new
metallocycle 11b were obtained. The corresponding Se
analogue 11c was equally accessible from 1c, and a
similar species 11a was probably formed from the
orthomanganated oxide 1a, although it could not be
separated from another species which ESMS indicated
incorporated two moles of Ph3P5O. However the shift
Acknowledgements
We thank Professor Ward T. Robinson, University of
Canterbury, and Associate Professor Cliff Rickard, Uni-
versity of Auckland, for collection of X-ray intensity
data, and Dr. R. Thomson for assistance with NMR
spectra. The New Zealand Vice Chancellors’ Commit-
tee and the William Georgetti Trust are acknowledged
of the n CO bands to higher frequencies, and the 31 P
NMR shift to 44 ppm from 64 ppm in the precursor, are
fully in accord with those for the sulfur and selenium
analogues so 11a is undoubtedly the corresponding
compound.
Ž
.
Ž
.
for scholarships GJD .
The new species 11 represent a unique series of
metallocyclic compounds, so the structure of the Se
analogue 11c was determined by X-ray crystallography.
The molecule is illustrated in Fig. 3. The six-membered
metallocyclic ring incorporates five different elements
—Mn, Se, S, P and C, with the ligand bound to the
manganese via the S and Se atoms. In contrast to the
planar five-membered ring in the precursor 1c, the
six-membered ring has an envelope conformation, with
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.
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w
w
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.
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.
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.
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.
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.
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Ž
.
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6
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.
w
x
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(
)
G.J. Depree et al.rJournal of Organometallic Chemistry 155 1998 281–291
291
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x
w
w
x
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x
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w x
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w x
Ž
.
Ž .
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