Journal of Inorganic and General Chemistry
www.zaac.wiley-vch.de
ARTICLE
Zeitschrift für anorganische und allgemeine Chemie
stronger charge transfer from the metal into the π*(CO) orbital 1694 (w), 1681 (w), 1667 (w), 1660 (w), 1651 (w), 1644 (w), 1633
(
1
(
(
4
w), 1614 (w), 1599 (w), 1574 (w), 1556 (w), 1538 (w), 1515 (w),
504 (w), 1495 (w), 1485 (w), 1463 (w), 1454 (w), 1434 (w), 1405
w), 1373 (w), 1299 (w), 1259 (w), 1117 (w), 1036 (w), 993 (w), 898
leading to smaller Mn–C bond lengths and slightly larger C–
O distances than observed for carbonyl ligands trans arranged
to each other. These complexes are significantly more stable
than the isostructural thiolates of the type [(OC) Mn(μ-SR)] ,
w), 875 (w), 829 (w), 799 (w), 693 (w), 683 (w), 555 (m), 515 (m),
4
2
–1
2 8 2
96 (m), 475 (m), 432 (w), 406 (w) cm . C40H36Mn O P , 815.53):
which degrade under liberation of carbon monoxide to tetranu-
calcd. C 58.84, H 4.44%; found: C 59.38, H 4.71%. M.p.: 509 K
(dec.).
[1]
clear [(OC) Mn(μ -SR)] .
3
3
4
4 2 2
Synthesis of {(CO) Mn[P(Ph)(cHex)]} (7): Mn (CO)10 (753 mg,
Experimental Section
1.89 mmol) was suspended in xylene (20 mL, mixture of isomers). In
another flask (cyclo-hexyl)phenylphosphane (798 mg, 4.15 mmol) was
dissolved in xylene (30 mL) and transferred at once to the Mn (CO)10
2
suspension. The reaction was heated to reflux for 4 h until gas evol-
ution ceased. While the reaction mixture was allowed to cool to room
temp., a yellow solid precipitated. Afterwards CO was bubbled through
the solution for 2 min. The precipitate was collected, washed with n-
General: All manipulations were carried out in an inert nitrogen atmo-
sphere using standard Schlenk techniques. The solvents were purified
and dried by standard techniques prior to use. The yields given are not
optimized. 1H, C{ H}, and P{ H} NMR spectra were recorded
13
1
31
1
with Bruker AC 200, AC 400, and AC 600 spectrometers. Chemical
shifts are reported in parts per million. [D ]THF was dried with so-
8
dium. Chemicals and solvents were commercially available and were
used as received without further purification. The synthesis of phos-
phanes that were not purchased, are described in the Supporting Infor-
mation.
hexane (3 mL) and dried in vacuo. Yield: 518 mg (0.72 mmol, 38%).
1
2 2
H NMR (400.075 MHz, CD Cl ): δ = 7.88–7.73 (m, 4 H), 7.60–7.29
(
m, 6 H), 2.34–2.15 (m, 6 H), 1.83–1.73 (m, 4 H), 1.61–1.51 (m, 4
31
H), 1.44–1.29 (m, 8 H). P NMR (161.953 MHz, CD
(
1
4
2
Cl
): δ = 136.1 (AA’X type),
35.8 (AA’X type), 134.3 (AA’X type), 129.6 (s), 129.5 (s), 128.0 (m),
3.5 (AA’X type), 43.2 (AA’X type), 30.5 (AA’X type), 30.3 (AA’X
2
): δ = –32.2
13
1
2 2
s). C{ H} NMR (100.599 MHz, CD Cl
Synthesis of {(CO)
.59 mmol) was suspended in xylene (20 mL, mixture of isomers). In
another flask bis(p-tolyl)phosphane (280 mg, 1.31 mmol) was dis-
solved in xylene (30 mL) and transferred at once to the Mn (CO)10
4 6 4 2 2 2
Mn[P(C H -4-Me) ]} (5): Mn (CO)10 (230 mg,
0
type), 28.0 (AA’X type), 27.9 (AA’X type), 26.0 (s), 25.9 (s). MS
+
+
(
[
(
(
DEI): m/z (%) = 688 [M – CO] (32), 604 [M – 4 CO] (60), 492
M
2
+
– 8 CO] (100). IR (neat solid): ν˜ = 3062 (w), 2931 (w), 2857
w), 2068 (w), 2038 (m), 1973 (s), 1963 (s), 1932 (vs), 1477 (w), 1450
w), 1431 (w), 1336 (w), 1295 (w), 1265 (w), 1202 (w), 1173 (w),
suspension. The reaction was heated to reflux for 4 h until gas evol-
ution ceased. After the reaction mixture was allowed to cool to room
temperature, CO was bubbled through the solution for 2 min. Re-
duction of the volume under reduced pressure yielded a yellow solid.
This precipitate was suspended in toluene (2 mL), filtered, washed
with toluene (another 2 mL) and dried in vacuo. Recrystallization from
1112 (w), 1080 (w), 1048 (w), 1001 (w), 915 (w), 890 (w), 850 (w),
8
19 (w), 740 (m), 722 (w), 696 (m), 551 (m), 524 (m), 499 (s), 484
–
1
(
s), 447 (s), 418 (s) cm . C32
2 8 2
H32Mn O P , 716.42): calcd. C 53.65,
H 4.50%; found: C 53.32, H 4.45%. M.p.: 463 K (dec.).
toluene gave single crystals suitable for X-ray diffraction studies.
Yield: 160 mg (0.21 mmol, 36%).
1
H
NMR (400.075 MHz,
Synthesis of {(CO)
249 mg, 0.62 mmol) was suspended in xylene (5 mL, mixture of iso-
mers). In another flask bis(4-dimethylaminophenyl)phosphane
350 mg, 1.29 mmol) was dissolved in xylene (20 mL) and transferred
at once to the Mn (CO)10 suspension. The reaction was heated to re-
4
Mn[P(C
6
H
4
-4-NMe
2
)
2
]}
2
2
(8): Mn (CO)10
3
1
[
(
(
(
[
(
8
D ]THF): δ = 7.64 (m, 8 H), 7.16 (m, 8 H), 2.29 (s, 12 H). P NMR
(
1
3
1
161.953 MHz, [D
101.599 MHz, [D
AA’X type), 129.5 (AA’X type), 20.8 (s). MS (DEI): m/z (%) = 732
8
]THF):
δ
=
–44.5 (s).
C{ H} NMR
8
]THF): δ = 139.3 (s), 138.1 (AA’X type), 134.0
(
2
+
+
+
M – CO] (24), 648 [M – 4 CO] (41), 536 [M – 8 CO] (100), 481
flux for 4 h until gas evolution ceased. During this time, a yellow solid
precipitated. After the reaction mixture was allowed to cool to room
temperature CO was bubbled through the solution for 2 min. The pre-
cipitate was collected, washed twice with xylene (5 mL) and dried in
+
22), 299 (53), 268 [M – 8 CO]0.5 (50), 237 (40), 211 (53), 146 (29),
5
1
5 (44). IR (neat solid): ν˜ = 2046 (m), 1976 (s), 1946 (m), 1937 (s),
495 (w), 1447 (w), 1394 (w), 1306 (w), 1263 (w), 1190 (w), 1081
(w), 1041 (w), 1016 (w), 802 (w), 542 (w), 513 (m), 505 (s), 488 (m),
vacuo. The yellow residue was recrystallized from THF. Yield: 378 mg
–1
475 (m), 447 (m), 434 (m), 416 (m) cm . C36
H
28Mn
2
O
8
P
2
(760.43):
1
(
(
[
0.43 mmol, 69%). H NMR (400.075 MHz, [D
8
]THF): δ = 7.60–7.53
calcd. C 56.86, H 3.71%; found: C 56.48, H 3.80%. M.p.: 479 K
dec.).
31
m, 8 H), 6.66 (m, 8 H), 2.92 (s, 24 H). P NMR (161.953 MHz,
(
13
1
D
8
]THF): δ = –53.9 (s). C{ H} NMR (100.599 MHz, [D
151.1 (s), 135.1 (AA’X type), 130.6 (AA’X type), 112.2 (AA’X
type), 40.1 (s). MS (Micro-ESI pos. in THF and methanol): m/z (%)
876.9 [M + H] (75), 848.9 [M + H - CO] (26), 820.9 [M + H -
CO] (32), 699.1 (37), 629.2 (62), 599.1 (100), 199.0 (43). IR (neat
8
]THF): δ
=
Synthesis of {(CO)
315 mg, 0.81 mmol) was suspended in xylene (20 mL, mixture of iso-
mers). In another flask bis(3,5-dimethylphenyl)phosphane (388 mg,
.60 mmol) was dissolved in xylene (5.4 mL) and transferred at once
to the Mn (CO)10 suspension. The reaction was heated to reflux for
h until gas evolution ceased. While the reaction mixture was allowed
4
Mn[P(C
6
H
3
-3,5-Me
2
)
2
]}
2
2
(6): Mn (CO)10
(
+
+
+
=
2
1
solid): ν˜ = 3088 (w), 2896 (w), 2857 (w), 2812 (w), 2041 (m), 1986
2
(
(
s), 1958 (s), 1927 (s), 1593 (m), 1545 (w), 1508 (m), 1443 (m), 1420
w), 1359 (m), 1318 (w), 1284 (w), 1231 (m), 1202 (m), 1173 (w),
4
to cool to room temperature, a yellow solid formed. The precipitate
was collected, washed with cold xylene (2 mL) and dried in vacuo.
The yellow residue was recrystallized from toluene. Yield: 290 mg
1121 (w), 1086 (m), 998 (w), 948 (m), 931 (w), 804 (m), 777 (w), 764
(
w), 751 (w), 718 (w), 694 (w), 650 (s), 633 (s), 550 (m), 529 (m),
16 (s), 493 (m), 432 (m), 417 (m), 407 (m) cm . C40H40Mn N O P ,
2 4 8 2
76.59): calcd. C 54.81, H 4.60, N 6.39%; found: C 54.69, H 4.95, N
.13%. M.p.: 458 K (dec.).
–1
5
8
6
+
(
0.36 mmol, 44%). MS (DEI): m/z (%) = 788 [M – CO] (27), 704
+
+
+
[M – 4 CO] (84), 676 [M – 5 CO] (9), 648 [M –6 CO] (43), 620
+
+
+
[M – 7 CO] (4), 592 [M – 8 CO] (100), 537 [M – 8 CO - Mn] (22),
+
+
4
82 [((Me
2
C
Me
6
H
3
)
2
+
P)
2
]
(5), 327 [MnP
2
(C
6
+
H
3
Me
] (16). IR (neat solid): pounds were collected with a Nonius KappaCCD diffractometer using
radiation. Data were corrected for
w), 1842 (w), 1799 (w), 1768 (w), 1747 (w), 1731 (w), 1714 (w), Lorentz and polarization effects; absorption was taken into account on
2
)
2
]
(71), 296
Crystal Structure Determination: The intensity data for the com-
[MnP(C
6
H
3
2
)
2
] (100), 241 [P(C Me )
6
H
3
2 2
ν˜ = 2918(w), 2851 (w), 2047 (w), 1997 (w), 1946 (m), 1923 (m), 1894 graphite-monochromated Mo-K
α
(
Z. Anorg. Allg. Chem. 2016, 508–514
512
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