Dinuclear potassium-chromium and potassium-tungsten carbonyl complexes

Article abstract of DOI:10.1002/ejic.200300585

The tetracarbonyl complexes [M(CO)₄{η²-(Ph ₂P)₂NH}] [M = Cr (1a), W (1b)] have been synthesised by reaction of M(CO)₆, Me₃NO·2H₂O, and (Ph₂P)₂NH. Subsequent

Full text of DOI:10.1002/ejic.200300585

FULL PAPER
Dinuclear Potassium-Chromium and Potassium-Tungsten Carbonyl Complexes
Vladimir Kirin[a] and Peter W. Roesky*[a]
Keywords: Chromium / Coordination chemistry / N Ligands / Potassium / Tungsten
The tetracarbonyl complexes [M(CO)4{η2-(Ph2P)2NH}] [M =
Cr (1a), W (1b)] have been synthesised by reaction of
compounds 2a,b are stable at room temperature. All four
compounds 1a,b and 2a,b were characterised by single-crys-
M(CO)6, Me3NO·2H2O, and (Ph2P)2NH. Subsequent treat- tal X-ray diffraction. Compounds 2a,b form infinite chains via
ment of complexes 1a,b with an excess of KH in THF at room
temperature yields the potassium salts [Cr(CO)4{η2-
(Ph2P)2N}K(THF)3]n (2a) and [W(CO)4{η2-(Ph2P)2N}K(THF)2]n
(2b), respectively, in almost quantitative yields. The ionic
isocarbonyl bridges in the solid state.
( Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim,
Germany, 2004)
Introduction
Anionic PϪN systems such as phosphinimides
(R2PNRЈ),[1,2] diphosphinoamides [(Ph2P)2N],[3Ϫ6] phos-
phoraneiminates (R3PN),[7Ϫ9] phosphiniminomethanides
[(RNPRЈ2)CH],[10] phosphiniminomethandiides [(RNPRЈ2)-
C][11] and diiminophoshphinates [(R2P(NRЈ)][12] have been
known for a long time and their chemistry has been inten-
sively studied over the years. Today there are numerous pap-
ers describing the synthesis, structure and reactivity of these
anions.[13] The PϪN anions are frequently used as ligands
in main group and transition metal chemistry.[7,14Ϫ16] Even
sodium and potassium have sometimes been used as coun-
terions for the PϪN anions, although the vast majority of
these compounds are lithium salts. These alkali-metal salts
are generally generated by deprotonation of the corre-
sponding neutral PϪN system, for example an aminophos-
phane, with butyllithium,[1] sodium[4] or potassium hy-
dride,[6] KOtBu,[5] or by other methods.[8] Ellermann et al.
have reported the deprotonation of a neutral PϪN ligand
that is coordinated to a transition metal fragment.[17,18] This
work was performed in situ by deprotonation of bis(diphen-
ylphosphanyl)aminechromium, -molybdenum or -tungsten
tetracarbonyl, [M(CO)4{η2-(Ph2P)2NH}] (M ϭ Cr, Mo, W)
with n-butyllithium. Due to its high sensitivity towards
moisture and air the obtained intermediate was not isolated
or characterised but further reacted at dry-ice temperature
with, for example, chlorophosphanes (Scheme 1). A similar
reaction has been performed on metal clusters having the
(Ph2P)2NH ligand in the coordination sphere.[19] Again, the
corresponding alkali metal species was not isolated. Other
groups have reported the deprotonation of cationic com-
plexes ligated by (Ph2P)2NH, which led to zwitterionic com-
pounds.[20]
Scheme 1
In this article we report on the synthesis and structural
characterisation of bis(diphenylphosphanyl)aminechrom-
ium and -tungsten tetracarbonyl, [M(CO)4{η2-(Ph2P)2NH}]
[M ϭ Cr (1a), W (1b)], along with details of further reac-
tions of these complexes with potassium hydride. These re-
actions lead, in a deprotonation reaction, to the corre-
sponding amidopotassium compounds [M(CO)4{η2-
(Ph2P)2N}K(THF)x]n [M ϭ Cr (2a), W (2b); x ϭ 2, 3],
which have been isolated and fully characterised by stand-
ard analytical/spectroscopic techniques. The structures of
2a,b have been confirmed by single-crystal X-ray diffraction
in the solid state. Compounds 2a,b form infinite chains via
isocarbonyl bridges in the solid state.
Results and Discussion
Synthesis
The tetracarbonyl complexes [M(CO)4{η2-(Ph2P)2NH}]
[M ϭ Cr (1a), W (1b)] have been synthesised previously by
reaction of M(CO)6 with (Ph2P)2NH in boiling do-
decane.[18,21] We made compounds 1a,b by reaction of
M(CO)6, Me3NO·2H2O, and (Ph2P)2NH in good yield at
room temperature (Scheme 2). Compound 1a was obtained
without significant amounts of by-product, whereas the
synthesis of 1b also yielded the pentacarbonyl complex
[W(CO)5{η1-(PhP2)2NH}]. Both 1a and 1b were character-
[a]
Institut für Chemie, Freie Universität Berlin,
Fabeckstraße 34Ϫ36, 14195 Berlin, Germany
Eur. J. Inorg. Chem. 2004, 1045Ϫ1050
DOI: 10.1002/ejic.200300585
 2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
1045

V. Kirin, P. W. Roesky
FULL PAPER
Scheme 2
ised by standard spectroscopic techniques. The observed Solid-State Structures
chemical shifts in the NMR spectra are in good agreement
with the literature data.[18,21]
The solid-state structures of 1a,b (Figures 1 and 2,
respectively) and 2a,b (Figures 3 and 4, respectively) were
established by single-crystal X-ray diffraction. The bond
lengths and angles of 1a,b are in the expected range. The
complex framework is similar to the structurally character-
ised molybdenum compound [Mo(CO)4{η2-(Ph2P)2NH}]·
CH3CN.[23] In contrast to compound 1a, in 1b one molecule
of acetone is bound via a hydrogen bond to the NϪH
function of the ligand.
The ionic complexes 2a,b show some surprising aspects
in the solid state. Both complexes form polymeric one-di-
mensional chains in the crystal. In Figure 5 a cutout of the
infinite chain of 2a is shown. The potassium cations are
bound to the amido nitrogen atom of one anion and to the
oxygen atom of a carbonyl group of a neighbouring anion.
Thus, a potassium isocarbonyl compound is formed. The
KϪN bond lengths are 271.1(2) pm (2a) and 273.6(3) pm
(2b) and the KϪO bond lengths are 264.9(2) pm (2a) and
270.2(3) pm (2b). There are no other structurally character-
ised KϪW and only a few KϪCr isocarbonyl complexes
The solid-state structures of both compounds were estab-
lished by single-crystal X-ray diffraction in order to learn
how further reactions at the ligand alter the complex frame-
work.
The potassium salts [Cr(CO)4{η2-(Ph2P)2N}K(THF)3]n
(2a) and [W(CO)4{η2-(Ph2P)2N}K(THF)2]n (2b) were ob-
tained in almost quantitative yield by treatment of the neu-
tral complexes 1a,b with an excess of KH in THF at room
temperature (Scheme 3). The ionic compounds 2a,b are
stable at room temperature even after several weeks the only
sign of decomposition in the solid state is the loss of THF
from the crystals. In solution we did not observe a possible
intermolecular reaction of the amido group with the car-
bonyl ligand.
Scheme 3
Compounds 2a and 2b were characterised by Raman, 1H,
13C{1H}, and 31P{1H} NMR spectroscopy and elemental
analysis. The 31P{1H} NMR resonances of 2a,b [δ ϭ Figure 1. Perspective ORTEP view of the molecular structure of
1a; thermal ellipsoids are drawn to encompass 50% probability;
58.7 ppm (2a), 8.07 ppm (2b)] are significantly shifted up-
hydrogen atoms are omitted for clarity; selected distances [pm] and
field relative to 1a,b [δ ϭ 96.9 ppm (1a), 46.1 ppm (1b)].
angles [°]: CrϪC1 189.1(2), CrϪC2 189.6(2), CrϪC3 185.2(2),
CrϪC4 186.4(2), CrϪP1 236.33(6), CrϪP2 234.50(6), NϪP1
169.6(2), NϪP2 168.8(2), O1ϪC1 114.4(2), O2ϪC2 113.9(2),
O3ϪC3 115.7(2), O4ϪC4 115.0(2); C1ϪCrϪC2 174.18(9),
C1ϪCrϪC3 90.39(9), C1ϪCrϪC4 86.62(9), C2ϪCrϪC3 86.08(9),
C2ϪCrϪC4 89.08(9), C3ϪCrϪC4 95.18(9), C1ϪCrϪP1 92.34(6),
C2ϪCrϪP1 92.25(6), C3ϪCrϪP1 165.00(6), C4ϪCrϪP1 99.70(7),
C1ϪCrϪP2 92.66(7), C2ϪCrϪP2 92.35(6), C3ϪCrϪP2 96.57(6),
C4ϪCrϪP2 68.23(7), P1ϪCrϪP2 68.58(2), P1ϪNϪP2 103.24(9)
1
Furthermore, an expected JP,W coupling in 2b of 168.7 Hz
is observed, which is about 40 Hz smaller than in 1b. Based
on earlier measurements of (Ph2P)2CH2 and [M(CO)4{η2-
(Ph2P)2CH2}] the signals in the 13C{1H} NMR spectra
could be clearly assigned in the phenyl and in the car-
bonyl region.[22]
1046
 2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjic.org
Eur. J. Inorg. Chem. 2004, 1045Ϫ1050

Dinuclear Potassium-Chromium and Potassium-Tungsten Carbonyl Complexes
FULL PAPER
Figure 2. Perspective ORTEP view of the molecular structure of
1b; thermal ellipsoids are drawn to encompass 50% probability;
hydrogen atoms are omitted for clarity; selected distances [pm] and
angles [°]: WϪC1 205(2), WϪC2 200(2), WϪC3 201.4(15), WϪP
249.2(4), NϪP 167.3(10), O1ϪC1 113(2), O2ϪC2 118(3), O3ϪC3
114(2); C1ϪWϪC2 176.8(9), C1ϪWϪC3 87.6(6), C2ϪWϪC3
90.3(6), C3ϪWϪC3Ј 97.9(8), C1ϪWϪP 92.3(5), C2ϪWϪP
90.3(6), C3ϪWϪP 98.7(4), C1ϪWϪPЈ 92.3(5), C2ϪWϪPЈ 90.3(6),
C3ϪWϪPЈ 163.4(4), PϪWϪPЈ 64.7(2), PϪNϪPЈ 105.7(9)
Figure 4. Perspective ORTEP view of the molecular structure of
2b; thermal ellipsoids are drawn to encompass 50% probability;
hydrogen atoms are omitted for clarity; selected distances [pm] and
angles [°]: WϪC1 202.3(4), WϪC2 202.0(4), WϪC3 200.2(4),
WϪC4 196.0(4), WϪP1 251.80(8), WϪP2 254.20(9), P1ϪN
166.0(3), P2ϪN 167.1(3), C1ϪO1 114.5(5), C2ϪO2 114.2(5),
C3ϪO3 113.9(5), C4ϪO4 117.3(5), KϪN1 273.6(3), KϪO4Ј
270.2(3), KϪO5 260.4(6), KϪO6 255.0(7); C1ϪWϪC2 174.16(15),
C1ϪWϪC3 87.0(2), C1ϪWϪC4 89.7(2), C2ϪWϪC3 90.03(2),
C2ϪWϪC4 85.56(15), C3ϪWϪC4 94.5(2), C1ϪWϪP1 94.23(12),
C2ϪWϪP1 89.99(12), C3ϪWϪP1 164.14(14), C4ϪWϪP1
101.34(11), C1ϪWϪP2 96.49(12), C2ϪWϪP2 89.10(11),
C3ϪWϪP2 103.78(14), C4ϪWϪP2 160.99(11), P1ϪWϪP2
60.37(3), O4ЈϪKϪO5 94.85(15), O4ЈϪKϪO6 82.4(2), O4ЈϪKϪN
92.24(10), P1ϪNϪP2 99.62(14), P1ϪNϪK 107.04(12), P2ϪNϪK
142.99(15)
Figure 3. Perspective ORTEP view of the molecular structure of
2a; thermal ellipsoids are drawn to encompass 50% probability;
hydrogen atoms are omitted for clarity; selected distances [pm] and
angles [°]: CrϪC1 189.2(2), CrϪC2 188.0(2), CrϪC3 185.5(2),
CrϪC4 182.2(2), CrϪP1 236.74(7), CrϪP2 239.80(6), P1ϪN
166.4(2), P2ϪN 167.3(2), C1ϪO1 114.2(3), C2ϪO2 114.2(3),
C3ϪO3 115.8(3), C4ϪO4 116.4(3), KϪN1 271.1(2), KϪO4Ј
264.9(2), KϪO5 266.8(3), KϪO6 266.3(3), KϪO7 270.3(3);
C1ϪCrϪC2 174.72(10), C1ϪCrϪC3 93.88(10), C1ϪCrϪC4
88.46(11), C2ϪCrϪC3 88.55(10), C2ϪCrϪC4 86.68(11),
C3ϪCrϪC4 94.07(11), C1ϪCrϪP1 90.05(7), C2ϪCrϪP1 88.86(7),
C3ϪCrϪP1 164.31(7), C4ϪCrϪP1 101.23(8), C1ϪCrϪP2
87.50(7), C2ϪCrϪP2 96.63(7), C3ϪCrϪP2 101.53(7), C4ϪCrϪP2
Figure 5. Solid-state structure of 2a showing the atom labelling
scheme, omitting hydrogen atoms; two units of infinite chain are
shown
lengths are also influenced. In the CO group (C4O4) that
forms the isocarbonyl bridge in 2a,b, the MϪC bond
lengths are shortened, whereas the CϪO bond lengths are
lengthened [MϪC: 186.4(2) pm (1a), 201.4(15) pm (1b),
182.2(2) pm (2a), 196.0(4) pm (2b); CϪO: 115.0(2) pm (1a),
164.12(8),
P1ϪCrϪP2
63.43(2),
O4ЈϪKϪO5
74.58(8),
O4ЈϪKϪO6 115.56(10), O4ЈϪKϪO7 85.35(10), O4ЈϪKϪN
12320.2534(8), P1ϪNϪP2 97.30(9), P1ϪNϪK 138.73(9), P2ϪNϪK
reported in the literature.[24] Furthermore, in 2a the potass- 114(2) pm (1b), 116.4(3) pm (2a), 117.3(5) pm (2b)].
ium atom is coordinated by three THF molecules and no
Due to the deprotonation of the (Ph2P)2NH ligand in
π-coordination of the phenyl rings is observed. In contrast, 2a,b the geometry of the (Ph2P)2N group is significantly
the potassium atom of compound 2b is surrounded by only different to that in 1a,b. The PϪNϪP angles of 2a,b
two THF molecules. Due to the vacant coordination sites [97.30(9)° (2a) and 99.62(14)° (2b)] are narrower than in
π-coordination of one phenyl ring of the (Ph2P)2N group is (Ph2P)2NH [118.9(2)°][25] and 1a,b [103.24(9)° (1a) and
seen. The different coordination modes of the potassium 105.7(9)° (1b)]. The PϪN distances of 2a,b [166.4(2) pm,
atoms in 2a and 2b cause significantly different OϪKϪN 167.3(2) pm (2a); 166.0(3) pm 167.1(3) pm (2b)], are slightly
bond angles [130.54(8)° (2a) and 92.24(10)° (2b)] in both shorter than those observed in 1a,b [169.6(2) pm, 168.8(2)
compounds. Furthermore, the MϪC and the CϪO bond pm (1a); 167.3(10) pm (1b)] and (Ph2P)2NH (168.2 pm). All
Eur. J. Inorg. Chem. 2004, 1045Ϫ1050
www.eurjic.org
 2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
1047

V. Kirin, P. W. Roesky
FULL PAPER
stored in vacuo over LiAlH4 in resealable flasks. CH2Cl2 and
CH3CN were distilled from over P2O5. Deuterated solvents were
obtained from Aldrich Inc. (all 99 atom% D). NMR spectra were
recorded on a Jeol JNM-LA 400 FT NMR spectrometer. Chemical
shifts are referenced to internal solvent resonances and are reported
relative to tetramethylsilane (1H and 13C) or 85% phosphoric acid
(31P NMR). Raman spectra were performed on a Bruker RFS 100.
Elemental analyses were carried out with an Elementar vario EL.
(Ph2P)2NH was prepared according to a literature procedure.[29]
the PϪN distances indicate a partial PϪN multiple-bond
character.[1a] Since the deprotonation does not significantly
influence the PϪN bond length we suggest that the negative
charge in 2a,b is basically located on the nitrogen atom.
This is supported by the NϪK contact in the solid state.
To the best of our knowledge only three other structurally
characterised heterobimetallic transition metalϪalkali me-
tal PϪN complexes have been reported in the literature,[26]
and none of them was generated by deprotonation of the
corresponding phosphinoamine compound.
The Raman spectra of compounds 1a,b and 2a,b were
recorded in the solid state. The spectrum of 1b (without
acetone) has been reported previously.[18] For 1b we observe
the same number of vibration modes, but at slightly differ-
ent wavenumbers. This may be a result of the additional
molecule of acetone. Based on earlier measurements on
[M(CO)4{η2-(Ph2P)2CH2}] (M ϭ Cr, W) the vibration
modes could be clearly assigned.[27] For the CϪO stretching
[Cr(CO)4{η2-(Ph2P)2NH}] (1a): a) A solution of Me3NO·2H2O
(1.14 g) in 11 mL of MeOH was added dropwise over 3 h to a sus-
pension of (Ph2P)2NH (1.78 g, 4.62 mmol) and Cr(CO)6 (1.08 g,
4.91 mmol) in 25 mL of CH2Cl2. After this time the reaction mix-
ture was stirred at room temperature for 18 h, filtered through silica
gel and the solvents evaporated under reduced pressure. The solid
residue was crystallised from hexane/CH2Cl2 mixture. Yield:
2.15 g (84.6%).
b) Upon addition of Me3NO·2H2O (0.23 g, 2.07 mmol) to a sus-
pension of Cr(CO)6 (0.42 g, 1.9 mmol) in 30 mL of MeCN at 0 °C,
vibration in 2a,b a noticeable shift to lower wavenumbers is a yellow colour steadily developed. After 10 min of vigorous stir-
ring, solid (Ph2P)2NH (0.75 g; 1.95 mmol) was added to the reac-
tion mixture. The resulting solution was stirred for 18 h at room
temperature and then at 70 °C for 5 h. The solvent was removed
under reduced pressure and the residue was chromatographed on
silica gel using hexane/acetone (4:1) as eluent. The bright-yellow
fraction (Rf ഠ 0.3) was isolated and recrystallised from hexane/
CH2Cl2 mixture. Yield: 0.63 g (60.3%). Raman (solid): ν˜ ϭ 3323
cmϪ1 (w, νNϪH), 3058 (m, νCϭC-H), 2018 (m, νCOax), 1915 (m,
νsymCOeq), 1859 (m, νasymCOeq), 1583 (w, νCϭC), 998 (s, νPC), 644
seen. This effect is especially noticeable for the symmetric
and asymmetric stretching vibration of the equatorial CO
groups (up to 56 cmϪ1 for 2a). The weakening of the CϪO
bond observed in the Raman spectra is in agreement with
the data of the single-crystal X-ray structures.
Conclusions
1
(w, δCO), 470 (m, νMC), 415 (m, νMC), 187 (s, νMP). H NMR
The (Ph2P)2NϪ anion, which was previously generated by
(CDCl3, 400 MHz, 25 °C): δ ϭ 7.51Ϫ7.23 (m, 20 H, Ph), 4.88 (t,
a deprotonation reaction of (Ph2P)2NH, has been used to 2JP,H ϭ 6.9 Hz, 1 H, NH) ppm. 13C NMR (C6D6, 100.4 MHz, 25
2
2
build alkali metal[3Ϫ6] titanium,[28] lanthanide,[6] and late
transition metal complexes and clusters.[19,20] Now we have
shown that the deprotonation of the tetracarbonyl com-
plexes [M(CO)4{η2-(Ph2P)2NH}] (M ϭ Cr, W) with potas-
sium hydride leads to bimetallic amidopotassiumϪ
isocarbonyl complexes [Cr(CO)4{η2-(Ph2P)2N}K(THF)3]n
(2a) and [W(CO)4{η2-(Ph2P)2N}K(THF)2]n (2b), in which
the transition metal is bound to the phosphorous atom and
°C): δ ϭ 228.8 (t, JP,C ϭ 8.7 Hz, COax), 221.7 (t, JP,C ϭ 13.2 Hz,
COeq), 139.3 (m, JP,C ϭ 19.9 Hz, Cipso), 130.5 (s, Cpara), 130.3 (m,
2JP,C ϭ 6.6 Hz, Cortho), 128.7 (m, JP,C ϭ 4.9 Hz, Cmeta) ppm. 31P
NMR (CDCl3, 161.7 MHz, 25 °C): δ ϭ 96.9 ppm. C28H21CrNO4P2
(549.47) C 61.21, H 3.85, N 2.55; found C 60.99, H 3.80, N 2.43.
[W(CO)4{η2-(Ph2P)2NH}] (1b) and [W(CO)5{η1-(Ph2P)2NH}]: A
mixture of W(CO)6 (2.7 g, 7.67 mmol), Me3NO·2H2O (0.86 g,
7.75 mmol), and (Ph2P)2NH (2.86 g, 7.43 mmol) in 100 mL of
the alkali metal is coordinated to the nitrogen atom. Com- MeCN was stirred at room temperature for 20 h and then heated
at 60 °C for 18 h. The resulting yellow-green solution was evapo-
rated to dryness and the residue was chromatographed on silica gel
using hexane/acetone/ethyl acetate (4:1:1) as eluent. The colourless
(Rf ഠ 0.7) and bright-yellow (Rf ഠ 0.7) fractions were isolated.
Recrystallisation of the first fraction from hexane/acetone gave
[W(CO)5{η1-(Ph2P)2NH}]·Me2CO (0.9 g, 17.1%). A second frac-
tion was recrystallised from hexane/ethyl acetate. The obtained
crystals were dissolved in toluene and the solution was evaporated
in vacuo to give [W(CO)4{η2-(Ph2P)2NH}].
plexes 2a,b form polymeric one-dimensional chains in the
solid state. The new amido compounds are stable at room
temperature and no intermolecular reaction of the amido
function with carbonyl group is observed. Based on the re-
sults of the single-crystal X-ray structures we suggest that
the negative charge is basically localised on the nitrogen
atom.
1b: Yield: 2.52 g (49.8%). Raman (solid, 1b·acetone): ν˜ ϭ 3054
cmϪ1 (m, νCϭC-H), 2018 (m, νCOax), 2923 (m, νCH), 1896 (m,
νCO), 1884 (m, νCO), 1872 (m, νCO), 1859 (m, νCO), 1699 (m,
νCO), 1586 (w, νCϭC), 998 (s, νPC), 456 (sh νMC), 441 (sh, νMC),
Experimental Section
General: All manipulations of air-sensitive materials were per-
formed with the rigorous exclusion of oxygen and moisture in
1
180 (s, νMP). H NMR (C6D6, 400 MHz, 25 °C): δ ϭ 7.46 (m, 8
2
flame-dried Schlenk-type glassware either on a dual manifold H), 6.95 (m, 12 H, Ph), 5.13 (t, JP,H ϭ 5 Hz, 1 H, NH) ppm. 13C
2
Schlenk line, interfaced to a high vacuum (10Ϫ3 Torr) line, or in an
NMR (C6D6, 100.4 MHz, 25 °C): δ ϭ 210.7 (dd, JP,C ϭ 22.7 Hz
2
argon-filled M. Braun glove box. Ether solvents (tetrahydrofuran and 7.0 Hz, COeq), 202.7 (t, JP,C ϭ 7.0 Hz, COeq), 138.6 (dd,
3
2
and diethyl ether) were predried over Na wire and distilled under
nitrogen from Na/K alloy benzophenone ketyl prior to use. Hydro-
carbon solvents (toluene and n-pentane) were distilled under nitro-
1JP,C ϭ 38.2 Hz; JP,C ϭ 6.8 Hz, Cipso), 130.7 (d, JP,C ϭ 15.6 Hz,
Cortho), 130.6 (s, Cpara), 128.7 (2JP,C ϭ 4.9 Hz, Cmeta) ppm. 31P
NMR (C6D6, 161.7 MHz, 25 °C): δ ϭ 46.1 (s, JP,W ϭ 208.1 Hz)
1
gen from LiAlH4. All solvents for vacuum-line manipulations were ppm.
1048  2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim www.eurjic.org
Eur. J. Inorg. Chem. 2004, 1045Ϫ1050

Dinuclear Potassium-Chromium and Potassium-Tungsten Carbonyl Complexes
FULL PAPER
1
W(CO)5{η1-(Ph2P)2NH}]: H NMR (C6D6, 400 MHz, 25 °C): δ ϭ
Ϫ0.466 e/AϪ3; 325 parameters (all non-hydrogen atoms were calcu-
2
7.55 (m), 7.26 (m), 6.91 (m) (20 H, Ph); 3.48 (t, JP,H ϭ 6.5 Hz, 1 lated as anisotropic; the positions of the H atoms were calculated
H, NH), 1.54 (s, 6 H, Me2CO) ppm. 13C NMR (C6D6, 100.4 MHz, for idealised positions) R1 ϭ 0.0368; wR2 ϭ 0.0874.
2
25 °C): δ ϭ 203.9 (Me2CO), 199.8 (d, JP,C ϭ 23.2 COtrans), 197.6 1b: Orthorhombic, space group Pbcm (no. 57); lattice constants
2
4
1
(dd, JP,C ϭ 7.83, JP,C ϭ 2.9 Hz, COcis), 141.0 (dd, JP,C ϭ 15.1,
a ϭ 938.84(4), b ϭ 1680.60(7), c ϭ 1920.77(7) pm, V ϭ 3030.6(2)
3JP,C ϭ 6.0 Hz), 139.1 (dd, JP,C ϭ 46.5, JP,C ϭ 3.9 Hz) (Cipso); ϫ 106 pm3, Z ϭ 4; µ(Mo-Kα) ϭ 3.956 mmϪ1; 2θmax. ϭ 56.00°; 3046
1
3
131.7 (dd, 2JP,C ϭ 12.8, 4JP,C ϭ 2.1 Hz), 131.4 (d, JP,C ϭ 21.5 Hz) (Rint ϭ 0.0526) independent reflections measured, of which 2830
2
3
(Cortho); 130.6 (d, JP,C ϭ 1.7 Hz), 129.36 (s) (Cpara); 128.7 (d, were considered observed with I Ͼ 2σ(I); max. residual electron
4
4JP,C ϭ 7.4 Hz), 128.6 (d, JP,C ϭ 9.9 Hz) (Cmeta); 30.1 (Me2CO) density 4.760 and Ϫ3.408 e/AϪ3; 183 parameters (all non-hydrogen
ppm. 31P NMR (C6D6, 161.7 MHz, 25 °C): δ ϭ 64.7 (d, JP,P
ϭ
atoms were calculated as anisotropic; the positions of the H atoms
were calculated for idealised positions) R1 ϭ 0.0801; wR2 ϭ
0.2098.
2
1
71, JP,W ϭ 267 Hz, coordinated P), 33.84 (d, uncoordinated P).
[Cr(CO)4{η2-(Ph2P)2N}K(THF)x] (x ؍ 2؊3) (2a): Solid 1a (0.50 g,
0.91 mmol) was added to a suspension of KH (70 mg, 1.75 mmol)
in 25 mL of THF. After stirring for 4 h at room temperature the
solvent was removed in vacuo and the resulting yellow powder was
crystallised from THF/n-pentane (1:4). After one day yellow crys-
tals were obtained. Yield: 0.69 g (95%). Raman (solid): 3056 cmϪ1
(m, νCϭC-H), 2983 (w, νCH), 2878 (w, νCH), 1986 (m, νCOax),
1879 (m, νsymCOeq), 1802 (m, νasymCOeq), 1584 (w, νCϭC), 998 (s,
νPC), 917 (w, νCϪC), 483 (m, νMC), 420 (m, νMC), 184 (m, νMP).
1H NMR ([D8]THF, 400 MHz, 25 °C): δ ϭ 7.73 (m, 8 H, Ph), 7.17
(m, 8 H, Ph) 7.09 (m, 4 H, Ph), 3.61 (m, 4 H, THF), 1.76 (m, 4 H,
THF) ppm. 13C NMR ([D8]THF, 100.4 MHz, 25 °C): δ ϭ 226.7
2a: Monoclinic, space group Cc (no. 9); lattice constants a ϭ
1601.3(3), b ϭ 1328.9(3), c ϭ 2056.8(4)pm, β ϭ 111.046(4)°, V ϭ
4084.9(13) ϫ 106 pm3, Z ϭ 4; µ(Mo-Kα) ϭ 0.508 mmϪ1; 2θmax.
ϭ
61.00°; 11604 (Rint ϭ 0.0156) independent reflections measured, of
which 10574 were considered observed with I Ͼ 2σ(I); max. re-
sidual electron density 0.814 and Ϫ0.405 e/AϪ3; 325 parameters
(all non-hydrogen atoms were calculated as anisotropic; the posi-
tions of the H atoms were calculated for idealised positions) Flack
parameter 0.005(13), R1 ϭ 0.0403; wR2 ϭ 0.1118.
¯
2b: Triclinic, space group P1 (no. 2); lattice constants a ϭ 969.1(2),
b ϭ 1113.5(2), c ϭ 1804.1(3) pm, α ϭ 94.348(3)°, β ϭ 97.122(3)°,
γ ϭ 113.016(3)°, V ϭ 108.075(3) ϫ 106 pm3, Z ϭ 2; µ(Mo-Kα) ϭ
3.415 mmϪ1; 2θmax. ϭ 60.00°; 10514 (Rint ϭ 0.0240) independent
reflections measured, of which 9368 were considered observed with
2
(COax), 221.4 (t, JP,C ϭ 13.2 Hz, COeq), 149.4 (JP,C ϭ 19.4 Hz,
Cipso), 130.7 (s, Cpara), 130.4 (Cortho), 127.7 (JP,C ϭ 5.8 Hz, Cmeta),
68.21 (s, THF), 26.36 (s, THF) ppm. 31P NMR ([D8]THF,
161.7 MHz, 25 °C): δ ϭ 58.7 ppm. C36H36CrKNO6P2 (x ϭ 2;
731.72): calcd. C 59.09, H 4.96, N 1.91; found C 58.04, H 4.77,
N 1.86.
I Ͼ 2σ(I); max. residual electron density 2.229 and Ϫ1.569 e/AϪ3
;
379 parameters (all non-hydrogen atoms were calculated aniso-
tropic; the positions of the H atoms were calculated for idealised
positions) R1 ϭ 0.0335; wR2 ϭ 0.0975.
[W(CO)4{η2-(Ph2P)2N}K(THF)2] (2b): Solid 1b (2.5 g; 3.67 mmol)
was added to a suspension of KH (237 mg, 5.92 mmol) in 50 mL
THF. After stirring at room temperature for 4 h the solvent was
removed in vacuo and the resulting yellow powder was crystallised
from THF/n-pentane (1:4). After one day yellow crystals were ob-
tained. Yield: 2.98 g (94%). Raman (solid): ν˜ ϭ 3055 cmϪ1 (m,
νCϭC-H), 2983 (w, νCH), 2877 (w, νCH), 1997 (m, νCOax), 1877
(m, νsymCOeq), 1802 (m, νasymCOeq), 1584 (w, νCϭC), 997 (s, νPC),
CCDC-217820 (1a), -217821 (1b), -217822 (2a), and -217823 (2b)
contain the supplementary crystallographic data for this paper.
These data can be obtained free of charge at www.ccdc.cam.ac.uk/
conts/retrieving.html [or from the Cambridge Crystallographic
Data Centre, 12, Union Road, Cambridge CB2 1EZ, UK; Fax:
(internat.) ϩ44-1223/336-033; E-mail: deposit@ccdc.cam.ac.uk].
1
918 (w, νCϪC), 483 (w, νMC), 442 (m, νMC), 184 (m, νMP). H
Acknowledgments
NMR ([D8]THF, 400 MHz, 25 °C): δ ϭ 7.69 (m, 8 H, Ph), 7.18
(m, 8 H, Ph) 7.08 (m, 4 H, Ph), 3.61 (m, 4 H, THF), 1.76 (m, 4 H,
THF) ppm. 13C NMR (C6D6, 100.4 MHz, 25 °C): δ ϭ 228.5
(COax), 221.63 (COeq), 148.8 (m, JP,C ϭ 23.09 Hz, Cipso), 127.9 (s,
This work was supported by the Deutsche Forschungsgemeinschaft
(Graduiertenkolleg: Synthetische, mechanistische und reaktions-
technische Aspekte von Metallkatalysatoren) and the Fonds der
Chemischen Industrie. Additionally, generous support from Prof.
Dr. H. Krautscheid (Universität Leipzig) and PD Dr. W.-D. Hun-
nius is gratefully acknowledged.
C
para), 130.8 (m, JP,C ϭ 6.4 Hz, Cortho), 127.7 (m, JP,C ϭ 5.2 Hz,
Cmeta), 68.2 (s, THF), 26.4 (s, THF). 31P NMR ([D8]THF,
161.7 MHz, 25 °C): 168.7 Hz) ppm.
8.07 (1JP,W
δ
ϭ
ϭ
C36H36KNO6P2W (863.58): calcd. C 50.07, H 4.20, N 1.62; found
C 49.95, H 4.17, N 1.54.
[1] [1a]
[1b]
M. T. Ashby, Z. Li, Inorg. Chem. 1992, 31, 1321Ϫ1322.
N. Poetschke, M. Nieger, M. A. Khan, E. Niecke, M. T. Ashby,
X-ray Crystallographic Studies of 1a, 1b, 2a and 2b: Crystals of 1a
and 1b were obtained from hexane/CH2Cl2 and hexane/acetone,
respectively. Crystals of 2a and 2b were grown from THF/n-pentane
(1:4). A suitable crystal was covered in mineral oil (Aldrich) and
mounted onto a glass fibre. The crystal was transferred directly to
the Ϫ73 °C cold N2 stream of a Stoe IPDS or a Bruker CCD
SMART 1000 diffractometer. Subsequent computations were car-
ried out on an Intel Pentium III PC.
[1c]
Inorg. Chem. 1997, 36, 4087Ϫ4093.
Z. Fei, R. Scopelliti, P.
J. Dyson, Inorg. Chem. 2003, 42, 2125Ϫ2130.
S. Wingerter, M. Pfeiffer, F. Baier, T. Stey, D. Stalke, Z. Anorg.
Allg. Chem. 2000, 626, 1121Ϫ1130.
[2]
[3] [3a]
J. Ellermann, M. Lietz, Z. Naturforsch., Teil B 1980, 35b,
[3b]
64Ϫ67.
H. Schmidbaur, S. Lautenschläger, F. H. Köhler, J.
Organomet. Chem. 1984, 271, 173Ϫ180.
J. Ellermann, M. Schütz, F. W. Heinemann, M. Moll, Z. Anorg.
Allg. Chem. 1998, 624, 257Ϫ262.
J. Ellermann, M. Schütz, F. W. Heinemann, M. Moll, Chem.
Ber./Recl. 1997, 130, 141Ϫ143.
P. W. Roesky, M. T. Gamer, M. Puchner, A. Greiner, Chem.
Eur. J. 2002, 8, 5265Ϫ5271.
K. Dehnicke, F. Weller, Coord. Chem. Rev. 1997, 158, 103Ϫ169.
T. Gröb, K. Harms, K. Dehnicke, Z. Anorg. Allg. Chem. 2000,
626, 1065Ϫ1072.
[4]
[5]
[6]
Data Collection and Refinement: SHELXS-97,[30] SHELXL-97.[31]
¯
1a: Triclinic, space group P1 (no. 2); lattice constants a ϭ
982.50(14), b ϭ 1160.8(2), c ϭ 1278.0(2) pm, α ϭ 106.368(4)°, β ϭ
94.523(4)°, γ ϭ 113.016(3)°, V ϭ 1257.3(3) ϫ 106 pm3, Z ϭ 2;
µ(Mo-Kα) ϭ 0.618 mmϪ1; 2θmax. ϭ 60.00°; 7271 (Rint ϭ 0.0316)
independent reflections measured, of which 4618 were considered
observed with I Ͼ 2σ(I); max. residual electron density 0.428 and
[7]
[8]
Eur. J. Inorg. Chem. 2004, 1045Ϫ1050
www.eurjic.org
 2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
1049

V. Kirin, P. W. Roesky
FULL PAPER
[9]
[22b]
S. Chitsaz, B. Neumüller, K. Dehnicke, Z. Anorg. Allg. Chem.
Trans. 1982, 1915Ϫ1921.
G. T. Andrews, I. J. Colquhoun,
W. J. Mc Farlane, Polyhedron 1983, 2, 783Ϫ790.
1999, 625, 9Ϫ10.
[10] [10a]
[23]
M. T. Gamer, P. W. Roesky, Z. Anorg. Allg. Chem. 2001,
M. Knorr, C. Strohmann, Organometallics 1999, 18, 248Ϫ257.
[24] [24a]
[10b]
627, 877Ϫ881.
R. P. Kamalesh Babu, K. Aparna, R.
D. J. Wink, J. R. Fox, N. J. Cooper, J. Am. Chem. Soc.
[24b]
McDonald, R. G. Cavell, Inorg. Chem. 2000, 39, 4981Ϫ4984.
1985, 107, 5012Ϫ5014.
M. D. Grillone, F. Benetollo, G.
[11] [11a]
C. M. Ong, D. W. Stephan, J. Am. Chem. Soc. 1999, 121,
2939. [11b] A. Kasani, R. P. Kamalesh Babu, R. McDonald, R.
G. Cavell, Angew. Chem. 1999, 111, 1580; Angew. Chem. Int.
Ed. 1999, 38, 1438.
F. T. Edelmann, Top. Curr. Chem. 1996, 179, 113Ϫ148.
O. J. Scherer, Multiple Bonds and Low Coordination in Phos-
phorous Chemistry, Georg Thieme Verlag, Stuttgart, 1990.
K. Dehnicke, M. Krieger, W. Massa, Coord. Chem. Rev. 1999,
182, 19Ϫ65.
T. Appleby, J. D. Woolins, Coord. Chem. Rev. 2002, 235,
121Ϫ140.
T. G. Wetzel, S. Dehnen, P. W. Roesky, Angew. Chem. 1999,
111, 1155Ϫ1158; Angew. Chem. Int. Ed. 1999, 38, 1086Ϫ1088.
J. Ellermann, W. Wend, J. Organomet. Chem. 1985, 281,
C29ϪC32.
Bombieri, A. Del Pra, J. Organomet. Chem. 1999, 575,
[24c]
193Ϫ199.
L. Xu, A. Ugrinov, S. C. Sevov, J. Am. Chem.
[24d]
Soc. 2001, 123, 4091Ϫ4092.
W.-q. Weng, A. M. Arif, R.
D. Ernst, Cluster Sci. 1996, 7, 629Ϫ641. [24e] J. W. Freeman, A.
M. Arif, R. D. Ernst, Inorg. Chim. Acta 1995, 240, 33Ϫ40.
H. Nöth, E. Fluck, Z. Naturforsch., Teil B 1984, 39, 744Ϫ753.
[12]
[13]
[25]
[26] [26a]
D. Fenske, B. Maczek, K. Maczek, Z. Anorg. Allg. Chem.
1997, 623, 1113Ϫ1120. [26b] G. Bai, H. W. Roesky, M. Nolteme-
[14]
[15]
[16]
[17]
yer, H.-G. Schmidt, J. Chem. Soc., Dalton Trans. 2002,
[26c]
2437Ϫ2440.
G. Bai, H. W. Roesky, M. Noltemeyer, H.-G.
Schmidt, Organometallics 2002, 21, 2789Ϫ2792.
H. Gäbelein, J. Ellermann, J. Organomet. Chem. 1978, 156,
389Ϫ402.
O. Kühl, T. Koch, F. B. Somoza, P. C. Junk, E. Hey-Hawkins,
D. Plat, M. S. Eisen, J. Organomet. Chem. 2000, 604, 116Ϫ125.
H. Noeth, L. Meinel, Z. Anorg. Allg. Chem. 1967, 349,
225Ϫ240.
G. M. Sheldrick SHELXS-97, Program for Crystal Structure
Solution, University of Göttingen, Germany, 1997.
G. M. Sheldrick, SHELXL-97 Program for Crystal Structure
Solution, University of Göttingen, Germany, 1997.
Received August 20, 2003
[27]
[28]
[29]
[30]
[31]
[18]
[19]
J. Ellermann, W. Wend, New. J. Chem. 1986, 10, 313Ϫ320.
M. Knorr, C. Strohmann, Eur. J. Inorg. Chem. 1998, 495Ϫ499.
[20] [20a]
´
I. Bachert, I. Bartusseck, P. Braunstein, E. Guillon, J. Rose,
[20b]
G. Kickelbick, J. Organomet. Chem. 1999, 588, 144Ϫ151.
J. Geicke, I. P. Lorenz, P. Murschel, K. Polborn, Z. Natur-
forsch., Teil B 1997, 52, 593Ϫ603.
[21]
J. Ellermann, W. H. Gruber, Z. Naturforsch., Teil B 1973, 28,
310Ϫ313.
Early View Article
Published Online January 28, 2004
[22] [22a]
I. J. Colquhoun, W. Mc Farlane, J. Chem. Soc., Dalton
1050
 2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjic.org
Eur. J. Inorg. Chem. 2004, 1045Ϫ1050