Fluxionality and phosphane arm-off reactions of octahedral ruthenium(II) complexes with the tripodal polyphosphane MeC(CH2PPh2)3

Article abstract of DOI:10.1002/(SICI)1099-0682(199803)1998:3<407::AID-EJIC407>3.0.CO;2-P

Structural fluxionality is apparent in the ¹ H- and ³¹P-NMR spectra of compounds of the type [Ru(L) (MeCN) (triPhos)](CF₃SO₃), 2-5, at 25°C, where L represents a diorganyldithiocarbamate or a heterocyclic κ²N,S coordinating thioamide. In contrast, complexes [Ru(Et₂NCS₂)(Y)-(triphos)]ⁿ⁺ (6, n = 1, Y = CO; 7, n = 0, Y = CN^- , 8, n = 0, Y = H^-) are stereochemically rigid in solution at this temperature, indicating that MeCN dissociation must occur for the crowded octahedral coordination spheres of 2-5. Reaction of [Ru(MeCN)₃(triphos)](CF₃SO₃)₂, 1, with Na(Et₂NCS₂) at a 1:2 molar ratio yields [Ru(Et₂NCS₂-κ²S)(Et₂NCS ₂-κS)(triphos)], 9, which slowly converts to [Ru(Et₂NCS₂-κ²S) ₂(triphosO-κ²P)], 10, on recrystallization from, ethanol/acetone under air [triphosO is O=P(Ph)₂CH₂C(CH₃)(CH₂PPh ₂)₂], A similar κ³P→κ²P arm-off dissociation leads to the formation of [Ru(mpy-κ²N,S)₂(triphosO-κ²P)] (13) and [Ru(mmim-κ²N,S)₂(triphosO-κ²P)] (14) (Hmpy = 2-mercaptopyridine, Hmmim = 2-mercapto-1-methylimidazole). Crystal structures are reported for [Ru(mbt-κ²N,S)(MeCN)(triphosκ³P)](CF ₃SO₃) (4) (Hmbt = 2-mercaptobenzothiazole), [Ru(mpym-κ²N,S)(mpym-κS)(triphos-κ³P)] (11) (Hmpym = 2-mercaptopyrimidine) and 14, the latter of which is present as the OC-6-13 isomer.

Full text of DOI:10.1002/(SICI)1099-0682(199803)1998:3<407::AID-EJIC407>3.0.CO;2-P

FULL PAPER
Fluxionality and Phosphane Arm-off Reactions of Octahedral Ruthenium(II)
Complexes with the Tripodal Polyphosphane MeC(CH2PPh2)3
Claudia Landgrafe, William S. Sheldrick*, and Marc Südfeld
Lehrstuhl für Analytische Chemie der Ruhr-Universität Bochum,
D-44780 Bochum, Germany
Received November 14, 1997
Keywords: Ruthenium / Phosphorus / Triphos complexes / Fluxionality / Arm-off dissociation
Structural fluxionality is apparent in the 1H- and 31P-NMR
spectra of compounds of the type [Ru(L)(MeCN)(tri-
10, on recrystallization from ethanol/acetone under air
[triphosO is O=P(Ph)2CH2C(CH3)(CH2PPh2)2]. similar
A
phos)](CF3SO3), 2Ϫ5, at 25°C, where L represents a diorga- κ3PǞκ2P arm-off dissociation leads to the formation of
nyldithiocarbamate or a heterocyclic κ2N,S coordinating
thioamide. In contrast, complexes [Ru(Et2NCS2)(Y)- κ2N,S)2(triphosO-κ2P)] (14) (Hmpy = 2-mercaptopyridine,
(triphos)]n+ (6, n = 1, Y = CO; 7, n = 0, Y = CNϪ; 8, n = 0, Y =
Hmmim = 2-mercapto-1-methylimidazole). Crystal structures
HϪ) are stereochemically rigid in solution at this tempera- are [Ru(mbt-κ2N,S)(MeCN)(triphos-
reported for
[Ru(mpy-κ2N,S)2(triphosO-κ2P)]
(13)
and
[Ru(mmim-
ture, indicating that MeCN dissociation must occur for the
crowded octahedral coordination spheres of 2Ϫ5. Reaction of
[Ru(MeCN)3(triphos)](CF3SO3)2, 1, with Na(Et2NCS2) at a 1:2
molar ratio yields [Ru(Et2NCS2-κ2S)(Et2NCS2-κS)(triphos)], 9,
which slowly converts to [Ru(Et2NCS2-κ2S)2(triphosO-κ2P)],
κ3P)](CF3SO3) (4) (Hmbt = 2-mercaptobenzothiazole), [Ru(m-
pym-κ2N,S)(mpym-κS)(triphos-κ3P)] (11) (Hmpym = 2-mer-
captopyrimidine) and 14, the latter of which is present as the
OC-6-13 isomer.
The employment of transition metal complexes of tri- cently reported[16][17] the stereochemical non-rigidity of the
podal polyphosphanes such as CH3C(CH2PPh2)3 (triphos) complex cations [RhL(MeCN)(triphos)]2ϩ in which L rep-
Ϫ
in homogeneous catalysis has attracted considerable inter- resents the bidentate diorganyldithiocarbamates R2NCS2
est[1][2][3][4].Although triphos is often regarded as a typical (R ϭ Et, Bz) or the heterocyclic thioamide mpymϪ
innocent ligand, whose neopentyl skeleton CH3C(CH2)3 al- (Hmpym ϭ 2-mercaptopyrimidine). Both CH3CN and
lows a relatively unstrained occupation of three facial sites phosphane arm-off dissociation processes can be proposed
in a square-pyramidal, trigonal-bipyramidal or octahedral to explain the fluxional behavior of such species. κ2P coor-
coordination sphere[5], dissociation of a phosphane arm to dinated complexes of the type [RhL2(triphos-κ2P)]ϩ (L ϭ
Ϫ
provide the more flexible κ2P binding mode has been impli- Et2NCS2Ϫ, Me2NCS2 mpymϪ) may be obtained on treat-
cated for a number of five-coordinate RhI and IrI com- ing the starting compound [Rh(MeCN)3(triphos)]3ϩ with
plexes[6][7][8][9][10][11][12][13]. The kinetic lability of MIϪP two equivalents of the potentially chelating ligands L.
bonds (M ϭ Rh, Ir) can also lead to structural fluxionality
These results prompted the present comparative study of
at higher temperatures. For instance dissociation of a tri- fluxionality and phosphane arm-off reactions for analogous
phosphane arm in [IrCl(CO)(triphos)] at room temperature isoelectronic octahedral RuII complexes. Our continuing
enables exchange between the two phosphorus environ- choice of diorganyldithiocarbamates and heterocyclic
ments and the 31P-NMR spectrum consists solely of a sin- thioamides as ligands L was motivated by their ability to
glet at δ ϭ Ϫ16.1[14]. An explanation for this behavior has coordinate in both a mono- or bidentate fashion[18][19], by
been sought in the marked reduction in ring strain that may the pronounced trans effect of their sulfur donor atoms and
be achieved on going from the facial κ3P geometry in an by their relatively restricted steric demands owing to a small
18eϪ trigonal-bipyramidal complex to the open κ2P ge- chelating angle of bite. The ambidentate thioamides
ometry of a square planar 16eϪ species[11][15]
.
mpymϪ, mpyϪ (Hmpy
ϭ 2-mercaptopyridine), and
The idealized PϪMϪP angles in octahedral RhIII or IrIII mmimϪ(Hmmim ϭ 2-mercapto-1-methylimidazole) were
complexes provide a relatively unstrained κ3P geometry for employed for a mechanistic study of isomer formation for
a tripodal polyphosphane, so that the energetic advantage complex cations of the type [RuL2(triphos-κ2P)]ϩ and
of an open κ2P coordination mode should be less pro- [RuL2(triphosO-κ2P)]ϩ [triphosO is OϭP(Ph)2CH2-
nounced than for five-coordinated MI complexes. However C(CH3)(CH2PPh2)2].
an arm-off dissociation has been implicated for the reaction
Results
Treatment of [Ru(MeCN)3(triphos)](CF3SO3)2 (1) with
of the octahedral RhIII complexes [RhL3(triphos)] (L ϭ Me,
[7][15]
1
H) with CO and H2
and H- and 31P-NMR evidence
have been presented for a κ3Pvκ2P equilibrium of the tri- selected anionic ligands L affords the octahedral complexes
phosphane ligand in solutions of [RhMe2(MeCN)- [Ru(Et2NCS2)(MeCN)(triphos)](CF3SO3) (2), [Ru(pyrdtc)-
(triphos)]ϩ at room temperature[11]. We ourselves have re- (MeCN)(triphos)](CF3SO3) (3) (pyrdtcϪ ϭ pyrrolidindithi-
Eur. J. Inorg. Chem. 1998, 407Ϫ414
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407

C. Landgrafe, W. S. Sheldrick, M. Südfeld
FULL PAPER
ocarbamate), [Ru(mbt)(MeCN)(triphos)](CF3SO3) (4) close to the idealised octahedral angle, both P(1)ϪRuϪP(3)
(Hmbt 2-mercaptobenzothiazole), and [Ru(mpym)- and P(2)ϪRuϪP(3) narrow markedly [84.7(1), 86.4(1)°]. A
ϭ
(MeCN)(triphos)](CF3SO3) (5) (schemes 1 and 2). Monon- marked trans influence of the thioamide sulfur atom is not
˚
uclear structures for the complex cations of 2Ϫ5 are con- apparent, indeed RuϪP(2) [2.302(2) A] is slightly shorter
˚
firmed by their highest FAB mass peaks, which each corre- than RuϪP(1) or RuϪP(3) [2.314(2), 2.307(2) A]. It is in-
spond to [M Ϫ MeCN Ϫ CF3SO3]ϩ. In contrast, the re- structive to contrast the formation of octahedral monoca-
duced steric demands of the facially coordinated cyclic tions in 2Ϫ5 with the recently reported five-coordinated
thioether 1,4,7-trithiacyclononane ([9]aneS3) allow the product [Rh(bdt)(triphos)]ϩ of the reaction of
adoption of tridentate µ-1κS:2κ2S,SЈ and µ-1κS:2κ2N,S [RhCl3(triphos)] with Na2(bdt) [bdt ϭ o-benzenedithiol-
bridging modes by respectively Me2NCS2Ϫ and mbtϪ in the ate(2Ϫ)][22]. The angle of bite of the κ2S coordinated o-
dinuclear
(CF3SO3)2
complexes
and [{Ru(µ-mbt)([9]aneS3)}2](CF3SO3)2
[{Ru(µ-Me2NCS2)([9]aneS3)}2]- benzenedithiolate ligand is no less than 20.3° wider than
[20]
[21]
.
that of the κ2N,S chelating 2-mercaptobenzothiazolate li-
The latter coordination pattern has also been reported for gand in 4. This finding suggests that the large Tolman cone
the organometallic half-sandwich complex [{Ru(µ- angle of at least 220° for the tripodal polyphosphane li-
mtz)(C6H6)}2Cl]Cl[18] (Hmtz ϭ 2-mercapto-2-thiazoline).
gand[23] will prevent the occupation of the potential sixth
coordination site in [Rh(bdt)(triphos)]ϩ.
Scheme 1. [Ru(Et2NCS2)(MeCN)(triphos)]ϩ cation of
2 and
[Ru(pyrdtc)(MeCN)(triphos)]ϩ cation of 3
Figure 1. Molecular structure of the cation of 4. Phenyl rings are
omitted for clarity[a]
Scheme 2. [Ru(mbt)(MeCN)(triphos)]ϩ cation of
4
and
[Ru(mpym)(MeCN)(triphos)]ϩ cation of 5
[a]
˚
Selected bond lengths [A] and angles [°]: RuϪP(1) 2.314(2),
RuϪP(2) 2.302(2), RuϪP(3) 2.307(2), RuϪS(1) 2.503(2), RuϪN(1)
2.242(6), RuϪN (61) 2.095(5), S(1)ϪC(1) 2.242(6), RuϪN(61)
2.095(5), S(1)ϪC(1) 1.714(8), S(2)ϪC(1) 1.723(8), S(2)ϪC(3)
1.735(9), S(1)ϪRuϪP(2) 168.9(1), N(1)ϪRuϪP(3) 169.9(2),
N(61)ϪRuϪP(1) 178.2(2), P(1)ϪRuϪP(2) 90.6(1), P(1)ϪRuϪP(3)
84.7(1), P(2)ϪRuϪP(3) 86.4(1), S(1)ϪRuϪN(1) 66.1(2).
Stereochemical non-rigidity is observed for each of the
monocations of 2Ϫ5 at room temperature. Whereas a dou-
blet and triplet at an integral ratio of 2:1 would be expected
for the magnetically inequivalent phosphorus atoms of the
diorganyldithiocarbamate complexes 2 and 3, their 31P-
NMR spectra in various solvents (CDCl3, MeOD, [D6]ace-
Figure 1 depicts the molecular structure of the mono- tone) consist of a single broad uncontoured resonance (in
cation of 4. As a result of the very small angle of bite CDCl3 2 δ ϭ 22Ϫ36, 3 δ ϭ 22Ϫ32) at ambient temperature
[S(1)ϪRuϪN(1) ϭ 66.1(2)°] of the coordinating hetero- [see Figure 2(a)]. As illustrated for 2 in Figure 2(b), cooling
cyclic thioamide mbtϪ, an acetonitrile ligand can occupy to Ϫ30°C provides the predicted spin pattern with resolved
the vacant sixth position of a coordination octahedron. doublets (2 δ ϭ 26.10, 3 δ ϭ 25.70) for the P atoms trans
However, the narrow S(1)ϪRuϪN(1) angle causes pro- to the diorganyldithiocarbamate S atoms and a triplet (2
nounced distortions in the geometry of the chelating poly- δ ϭ 27.44, 3 δ ϭ 28.56) for the single P atom trans to aceto-
phosphane cage. Whereas P(1)ϪRuϪP(2) [90.6(1)°] remains nitrile. Each of the phosphorus atoms in the thioamide-con-
408
Eur. J. Inorg. Chem. 1998, 407Ϫ414

Complexes with the Tripodal Polyphosphane MeC(CH2PPh2)3
FULL PAPER
taining cations of 4 and 5 should generate its own separate Figure 3. 31P-NMR spectrum of 4 in CDCl3: (a) at room tempera-
31P-NMR resonance. In fact, the fluxional behavior of 4 in
ture, (b) at Ϫ30°C.
CDCl3 solution leads to the observation of only two broad
resonances at room temperature [Figure 3(a)]. Although
three signals can be identified for 5 at this temperature, they
are likewise broad and without fine structure. As may be
seen for 4 in Figure 3(b), cooling to Ϫ30°C once again pro-
vides stereochemical rigidity and three individual triplets (4
δ ϭ 20.92, 31.52, 36.53; 5 δ ϭ 19.89, 28.05, 37.59) appear in
1
the 31P-NMR spectrum at this temperature. The H-NMR
spectra of 2Ϫ5 are also in accordance with cation fluxional-
ity at room temperature. For instance, whereas only a single
broad resonance at δ ϭ 2.43 can be observed for the triphos
CH2 protons of 2 at 25°C, three multiplets can be identified
in CDCl3 solution at Ϫ30°C: δ ϭ 2.19, 2.30, 2.68). Restric-
ted rotation about the diorganyldithiocarbamate CϪN
bond also leads to the observation of two signals for the
ethyl CH2 protons of this cation at Ϫ30°C (δ ϭ 3.64, 3.84),
which then coalesce to a single resonance (δ ϭ 3.82) at am-
bient temperature.
Figure 2. 31P-NMR spectrum of 2 in CDCl3: (a) at room tempera-
ture, (b) at Ϫ30°C.
changed on raising the solution temperature from Ϫ30°C
to 25°C and, therefore, provide no evidence for a rapid
acetonitrile exchange process. This finding prompted us to
investigate whether fluxionality is also a general phenom-
enon for other sterically crowded RuII complexes of the type
[Ru(Et2NCS2)(Y)(triphos)]nϩ (6, n ϭ 1, Y ϭ CO; 7, n ϭ 0,
Y ϭ CNϪ 8, n ϭ 0, Y ϭ HϪ) depicted in Scheme 3. How-
1
ever, H and 31P NMR spectra for 6Ϫ8 in [D6]DMSO or
CDCl3 at both 25°C or 60°C indicate that these non-aceto-
nitrile complexes are, in fact, all stereochemically rigid in
solution. Pronounced highfield shifts are apparent for the
P atom in trans position to the monodentate ligand Y in
both 6 (6, L ϭ CO, δ ϭ 3.54) and the hydride complex 8
(δ ϭ 5.29).
The implicated lack of triphos arm-off dissociation for
RuII complexes of the type [Ru(L)(Y)(triphos)]nϩ in solu-
tion led us to investigate whether κ2P coordinated triphos
complexes with a dangling phosphone arm can be stabilized
by the presence of an excess of a small bite chelating ligand
such as Et2NCS2Ϫ, mpymϪ, mpyϪ, or mmimϪ. A facial
replacement of one binding P atom is observed when
Both CH3CN and phosphane arm-off dissociation can be [Rh(MeCN)3(triphos)]3ϩ is treated with two equivalents of
discussed as possible mechanisms to explain the stereo- bidentate ligands L, thereby yielding[16][17] κ2P coordinated
chemical
non-rigidity
of
the
cations
[Ru(L)- complexes
such
as
ϭ
[Rh(R2NCS2-κ2S)2(triphos-
Et, Me) or [Rh(mpym-
(MeCN)(triphos)]ϩ of 2Ϫ5 in solution at 25°C. The posi- κ2P)][CF3SO3] (R
tion and width of the sharp MeCN singlets in the 1H-NMR κ2N,S)2(triphos-κ2P)][CF3SO3]. In contrast, retention of a
spectra of these complexes in CDCl3 (Ϫ30°C: 2 δ ϭ 1.80, κ3S facial coordination mode has been reported for the cy-
3 δ ϭ 1.87, 4 δ ϭ 1.87, 5 δ ϭ 1.61) remain effectively un- clic thioether [9]aneS3 in [Rh(mpym-κ2N,S)(mpym-
Eur. J. Inorg. Chem. 1998, 407Ϫ414
409

C. Landgrafe, W. S. Sheldrick, M. Südfeld
FULL PAPER
Scheme 3. [Ru(Et2dtc)(CO)(triphos)]ϩ cation of 6 and molecules 38Ϫ40, the phosphorus resonances of 9 (δ ϭ 19.06, 32.37)
[Ru(Et2dtc)(L)(triphos)]ϩ [(L ϭ CN (7), H (8)]
are now completely absent. It may be assumed that the driv-
ing force for the κ3PǞκ2P arm-off reaction will be provided
by the thermodynamic advantage of κ2S chelation of both
Ϫ
Et2NCS2 ligands. However, this process proceeds much
more slowly than for the analogous RhIII complexes, for
which intermediate products of the type [Rh(R2NCS2-
κ2S)(R2NCS2-κS)(triphos-κ3P)]ϩ cannot be isolated[16]
.
Scheme 4. [Ru(Et2dtc)2(triphos)] (9) and [Ru(Et2dtc)2(triphosO)]
(10)
κS)([9]aneS3-κ3S)][CF3SO3][19] and [Ru(mbt-κ2N,S)(mbt-
κS)([9]aneS3-κ3S][21]. The presence of both mono- and bi-
dentate dimethyldithiocarbamate ligands has been con-
firmed for the organometallic half-sandwich complex
[Rh(η5-C5Me5)(Me2NCS2-κ2S)(Me2NCS2-κS)][24]
.
Treatment of 1 with Na(Et2NCS2) at a 1:2 or 1:3 ratio
affords the κ3P-triphos coordinated complex [Ru(Et2NCS2-
The reaction of 1 with 2 equivalents of the ambidentate
κ2S)(Et2NCS2-κS)(triphos-κ3P)] (9), whose structure heterocyclic thioamides mpymϪ, mpyϪ, and mmimϪ was
(Scheme 4) was established by elemental analysis, FAB mass studied to provide information on possible preferred isomer
spectrometry, and NMR spectroscopy. 9 exhibits a doublet formation for products of the type [Ru(L)2(triphosO-κ2P)].
at δ ϭ 19.06 for the P atoms trans to the κ2S coordinated As for diethyldithiocarbamate Et2NCS2Ϫ, κ3P-triphos co-
chelating ligand and a triplet at δ ϭ 32.37 for the remaining ordinated
complexes
[Ru(mpym-κ2N,S)(mpym-κS)-
Ϫ
P atom trans to the monodentate Et2NCS2 ligand. The (triphos)] (11) and [Ru(mpy-κ2N,S(mpy-κS)(triphos)] (12)
presence of a singlet at δ ϭ ca. Ϫ25 to Ϫ30 would be can be isolated in high yield at room temperature. Both are
characteristic for the P atom of a free dangling phosphane once again stereochemically rigid in solution at 25°C and
arm in a κ2P coordinated complex[16][17]. Both the 1H- and may be characterized by their FAB MS basis peaks [M]ϩ
31P-NMR spectra are in accordance with stereochemical and the presence of three 31P NMR triplets in the range
rigidity of 9 in CDCl3 solution at 25°C. However attempts δ ϭ 21.5Ϫ29.2. In contrast to 10 or 12, the 2-mercaptopyri-
to recrystallize 9 from an ethanol/acetone solution under midinate complex 11 is stable in solution under air and may
air led to formation of the κ2P coordinated complex be recrystallized from CHCl3/MeOH to afford crystals suit-
[Ru(EtNCS2-κ2S)2(triphosO-κ2P)] (10) over a period of 14 able for X-ray analysis (Figure 4). The small angle of bite
d in relatively good yield (50%). The oxidation of the unco- [S(1)ϪRuϪN(1) 65.9(2)°] of the coordinating thioamide
ordinated P atom is confirmed by the observation of a FAB causes a marked narrowing of the opposite P(2)ϪRuϪP(3)
MS basis peak m/z for [M]ϩ at 1038, by a characteristic IR angle to 85.0(1)°. As a result of the weaker trans influence
absorption band for ν˜(PO) at 547 cmϪ1, and by the pres- of N, the RuϪP(2) distance of 2.291(2) A is somewhat
˚
ence of a typical 31P-NMR resonance at δ ϭ 26.86, a value shorter than for the remaining triphos P atoms [2.301(2),
very similar to that of 27.18 found for the analogous RhIII 2.322(2) A]. On leaving 12 to stand in CHCl3 solution un-
˚
complex [Rh(Et2NCS2-κ2S)2(triphosO-κ2P)]Cl[16]. It is pos- der air a color change from yellow to orange may be fol-
sible to follow the required κ3PǞκ2P arm-off reaction of lowed over a period of 3 d and the triphosO-κ2P complex
the initially κ3P coordinated triphos in 9 by 31P NMR spec- [Ru(mpy-κ2N,S)2(triphosO-κ2P)] (13) may be isolated in ef-
troscopy. After 2d, respective singlets at δ ϭ Ϫ26.00 and fectively quantitative yield after 14 d. Rapid oxidation of
26.86 for the dangling phosphorus atom in κ2P coordinated the dangling phosphane arm is typical for analogous κ2P
triphos and its oxidation product triphosO in the final coordinated RhIII complexes[16][17] and has also been re-
product 10 can be identified. These resonances also appear ported for square-planar RhI and NiII complexes[6][25]
.
in the 31P-NMR spectrum of the mixture of Whereas 12 exhibits three triplets for its magnetically in-
[Ru(Et2NCS2)2(triphos-κ2P)] and [Ru(Et2NCS2)2(triphos- equivalent P (δ 21.55, 26.60, 29.17 ppm) atoms, a singlet at
O-κ2P)] present after 7 d in a CDCl3 solution of 9 exposed δ ϭ 25.89 and an AB pattern at δ ϭ 42.45 for two nuclei
to air. Whereas overlapping signals for the coordinated P with closely similar chemical shifts were recorded for 13.
atoms of these complexes may be located in the range δ ϭ The position of the former resonance is typical for the oxid-
410
Eur. J. Inorg. Chem. 1998, 407Ϫ414

Complexes with the Tripodal Polyphosphane MeC(CH2PPh2)3
FULL PAPER
ized phosphorus of triphosO and the latter spin system Figure 5. Molecular structure of 14. Phenyl rings are omitted for
clarity[a]
would be expected for either the OC-6-22 (N trans to N) or
OC-6-13 (S trans to S) isomer but not the third possible
OC-6-32 (S trans to N) isomer of Scheme 6. Although at-
tempts to obtain crystals suitable for X-ray analysis re-
mained unsuccessful, the molecular structure of the anal-
ogous κ2P-triphosO complex [Ru(mmim-κ2N,S)2(triphosO-
κ2P)] (14) was determined. As previously also established
for two RhIII complexes [Rh(mpy-κ2N,S)2(triphosO-
κ2P)]Cl[16]
and
[Rh(mmim-κ2N,S)2(triphosO-κ2P)]-
[CF3SO3][17], 14 is present as the OC-6-13 isomer. The ob-
servation of individual resonances for the coordinated tri-
phosO P atoms (δ ϭ 47.8, 49.9) and the duplication of the
mmimϪ methyl singlet (δ ϭ 2.94, 2.98) and aromatic proton
doublets (δ ϭ 5.93, 6.09, 6.52, 6.61) indicates that the mo-
lecular geometry of 14 must deviate significantly from an
idealized C2 symmetry. This is confirmed by the observed
distortions in the RuII coordination sphere of the X-ray
structure (Figure 5). In view of the similarity of the 31P
NMR data for 13 and 14 it seems reasonable to assume that
the former complex is also present as the OC-6-13 isomer
with S atoms in trans position to one another.
Figure 4. Molecular structure of 11. Phenyl rings are omitted for
clarity[a]
[a]
˚
Selected bond lengths [A] and angles [°]: RuϪP(1) 2.239(5),
RuϪP(3) 2.242(5), RuϪS(1) 2.480(6), RuϪS(2) 2.457(6), RuϪN(1)
2.155(4),
RuϪN(3)
2.21(2),
N(3)ϪRuϪP(1)
172.8(5),
N(1)ϪRuϪP(3) 169.6(5), S(1)ϪRuϪS(2) 156.1(2), P(1)ϪRuϪP(3)
89.2(5), N(1)ϪRuϪS(1) 66.9(5), N(3)ϪRuϪS(2) 68.1(5).
Scheme 5. [Ru(mpym)2(triphos)] (11) and [Ru(mpy)2(triphos)] (12)
[a]
˚
Selected bond lengths [A] and angles [°]: RuϪP(1) 2.301(2),
RuϪP(2) 2.291(2), RuϪP(3) 2.322(2), RuϪS(1) 2.488(2), RuϪS(22)
2.451(2),
RuϪN(1)
2.142(7),
S(22)ϪRuϪP(1)
168.3(1),
N(1)ϪRuϪP(2) 170.3(1), S(1)ϪRuϪP(3) 170.3(1), P(1)ϪRuϪP(2)
89.3(1), P(1)ϪRuϪP(3) 91.0(1), P(2)ϪRuϪP(3) 85.0(1),
S(1)ϪRuϪN(1) 65.9(2).
Our present results indicate that the fluxionality of octa-
hedral RuII complexes [Ru(L)(MeCN)(triphos-κ3P)]ϩ of bi-
dentate ligands LϪ results from a facile acetonitrile dis-
sociation to
a
five-coordinate species [Ru(L)(triphos- plexes such as [Ru(Et2NCS2-κ2S)(Et2NCS2-κS)(triphos-
κ3P)]ϩ. In contrast to the analogous acetonitrile complexes, κ3P)] (9) or the analogous mpymϪ and mpyϪ complexes 11
κ3P-triphos compounds of the type [Ru(L)(Y)(triphos- and 12. However 9 and 12 do exhibit a slow arm-off phos-
κ3P)]nϩ (n ϭ 1, Y ϭ CO; n ϭ 0, Y ϭ CNϪ, HϪ) are stereo- phane dissociation and subsequent oxidation to afford the
chemically rigid in solution at both 25°C and 60°C. Arm- thermodynamically favorable bis-chelates [Ru(Et2NCS2-
off κ3PǞκ2P reactions are apparently less favorable for κ2S)2(triphosO-κ2P)] (10) and [Ru(mpy-κ2N,S)2(triphosO-
RuII than for RhIII, thereby allowing the isolation of com- κ2P)] 13. As 13 and 14 are both formed from κ3P-triphos
Eur. J. Inorg. Chem. 1998, 407Ϫ414
411

C. Landgrafe, W. S. Sheldrick, M. Südfeld
FULL PAPER
[Ru(pyrdtc)(MeCN)(triphos)](CF3SO3) (3): The preparation
of 3 was performed using 1 and NH4(pyrdtc) (pyrdtcϪ ϭ pyrrolidi-
nedithiocarbamate) under conditions analogous to those for 2.
Yield 119.5 mg (75%). Ϫ FAB MS, m/z (%): 872 (100) [M Ϫ MeCN
Scheme 6. Possible isomers of [Ru(mpy)2(triphosO)] 13
1
Ϫ CF3SO3]ϩ. Ϫ H NMR (CDCl3, Ϫ30°C): δ ϭ 58 (s, 3 H, CH3
triphos), 1.87 (s, 3 H, MeCN), 1.97, 2.08, 2.14 (3ϫ2 H, 3 m, CH2
pyrdtcϪ and triphos), 2.32 (m, 2 H, CH2 triphos), 2.64 (m, 2 H,
CH2 triphos), 3.64 (m, 4 H, CH2 pyrdtcϪ), 6.87Ϫ7.39 (m, 30 H,
Ph triphos). Ϫ 31P NMR (CDCl3, Ϫ30°C): δ ϭ 5.70 (d, 2 P, trans to
pyrdtcϪ), 28.56 (t, 1 P, trans to MeCN). Ϫ C49H50F3N2O3P3RuS3
(1062.1): calcd. C 55.4, H 4.7, N 2.6; found C 54.5, H 5.1, N 2.3.
[Ru(mbt)(MeCN)(triphos)](CF3SO3) (4): 2-Mercaptobenzo-
thiazole Hmbt (25.2 mg, 0.15 mmol) was dissolved in 10 ml MeOH
in the presence of 0.15 mmol 1  NaOH. After addition of 1 (172.0
mg, 0.15 mmol) the reaction mixture was heated for 2 h at reflux
and subsequently filtered; the volume of the red-brown solution
was then reduced to 1 ml. Standing at Ϫ18°C led to crystallization
of yellow-brown prisms of 4·1/2 MeOH suitable for X-ray analysis.
Yield 120.2 mg (73%). Ϫ FAB MS, m/z (%): 892 (100) [M Ϫ MeCN
1
Ϫ CF3SO3]ϩ. Ϫ H NMR (CDCl3, Ϫ30°C): δ ϭ 1.59 (s, 3 H, CH3
triphos), 1.87 (s, 3 H, MeCN), 2.27 (m, 2 H, CH2 triphos), 2.46
(m, 3 H, CH2 triphos), 2.60 (m, 1 H, CH2 triphos), 6.30 (d, 1 H,
mbt), 6.80Ϫ7.39 (m, 32 H, Ph triphos and mbt), 7.68 (d, 1 H, mbt).
complexes it may be assumed that the first reaction stage
will involve a slow κ3P v κ2P dissociation. This must be
followed by rapid isomerisation of the five-coordinated in-
termediate to allow nucleophilic attack of the N atom of
the previously κS coordinated thioamide at a site trans to a
κ2P-triphos phosphorus. The resulting octahedral complex
will then exhibit the observed OC-6-13 geometry. Relief of
steric crowding and the energetic advantage of the associ-
ated formation of a second κ2S or κ2S,N chelate may be
presumed to provide the driving force behind such a triphos
arm-off dissociation.
Ϫ
31P NMR (CDCl3, Ϫ30°C): δ ϭ 20.92 (t, 1 P), 31.52 (t, 1 P),
36.43 (t, 1 P). Ϫ C51H46F3N2O3P3RuS3 ·0.5 MeOH (1098.1): calcd.
C 56.3, H 4.4, N 2.6; found C 55.9, H 4.4, N 2.4.
[Ru(mpym)(MeCN)(triphos)](CF3SO3) (5): The preparation
of 5 was carried out with 1 and 2-mercaptopyrimidine (Hmpym)
in a manner analogous to that employed for 4. Yield 126.3 mg
(82%). Ϫ FAB MS, m/z (%): 986 (2) [Mϩ], 837 (100) [M Ϫ MeCN
Ϫ CF3SO3]ϩ. Ϫ 1H NMR (CDCl3, Ϫ30°C): δ ϭ 1.61 (s, 3 H,
MeCN), 1.63 (s, 3 H, CH3 triphos), 2.05 (m, 1 H, CH2 triphos),
2.26 (m, 2 H, CH2 triphos), 2.78 (m, 3 H, CH2 triphos), 6.60Ϫ7.56
(m, 31 H, Ph triphos and mpym), 7.78 (d, 1 H, mpym), 8.45 (d, 1
H, mpym). Ϫ 31P NMR (CDCl3, Ϫ30°C): δ ϭ 19.89 (t, 1 P), 28.05
(t, 1 P), 37.59 (t, 1 P). Ϫ C48H45F3N3O3P3RuS2 (1027.0): calcd. C
56.1, H 4.4, N 4.1; found C 55.4, H 5.1, N 3.6.
Experimental Section
Where not otherwise stated reactions were performed under Ar
in carefully dried solvents. Ϫ FAB MS: Fisons VG Autospec with
3-nitrobenzyl alcohol as the matrix. Ϫ FT-IR: KBr, Perkin-Elmer
1760. Ϫ 1H and 31P{1H} NMR: Bruker AM 400; chemical shifts
are reported as δ values relative to the signal of the deuterated
solvent (for 1H) or relative to 85% H3PO4 as external standard
(for 31P). Ϫ Elemental analyses: Carlo Erba 1106. Ϫ The starting
compound [Ru(MeCN)3(triphos)][CF3SO3] (1) was prepared ac-
cording to the literature procedure[26] from RuCl3 ·x H2O, which
was a gift from Degussa AG.
[Ru(Et2NCS2)(CO)(triphos)](CF3SO3) (6): CO was bubbled
through a solution of 2 (119.7 mg, 0.11 mmol) in 20 ml CH2Cl2
leading to loss of the initial deep red color. After filtration and
reduction in volume to 2 ml addition of 10 ml of diethyl ether led
to precipitation of 6 which was centrifuged off and dried in vac-
uum. Yield 87.9 mg (76%). Ϫ FAB MS, m/z (%): 902 (26) [M Ϫ
CF3SO3]ϩ, 874 (87) [M Ϫ CO Ϫ CF3SO3]ϩ. Ϫ 1H NMR
([D6]DMSO): δ ϭ 1.14 (t, 6 H, CH3 Et2NCS2), 1.70 (s, 3 H, CH3
triphos), 2.53Ϫ2.85 (m, 6 H, CH2 triphos), 3.54 (m, 2 H, CH2
Et2NCS2), 3.71 (m, 2 H, CH2 Et2NCS2), 6.94Ϫ7.49 (m, 30 H, Ph
triphos). Ϫ 31P NMR ([D6]DMSO): δ ϭ 3.54 (t, 1 P, trans to CO),
21.20 (d, 2 P, trans to Et2NCS2). Ϫ IR: ν˜ ϭ 2002 s cmϪ1 (CO). Ϫ
C48H49F3NO4P3RuS3 (1051.1): calcd. C 54.9, H 4.7, N 1.3; found
C 53.4, H 4.6, N 1.7.
[Ru(Et2NCS2)(MeCN)(triphos)](CF3SO3)
(2):
Na(Et2-
NCS2)·3 H2O (33.8 mg, 0,15 mmol) was added to a solution of 1
(172.0 mg, 0.15 mmol) in 10 ml of MeOH and the reaction mixture
heated at reflux for 3 h. After filtration the red solution was re-
duced in volume to 3 ml and left to stand at room temperature to
afford a yellow precipitate of 2 within 24 h. Recrystallisation from
[Ru(CN)(Et2NCS2)(triphos)] (7): NaCN (4.4 mg, 0.09 mmol)
ethanol provided 2·0.5 C2H5OH. Yield 111.0 mg (68%). Ϫ FAB was added to 1 (95.2 mg, 0.09 mmol) in 10 ml of ethanol and the
MS, m/z (%): 874 (100) [M Ϫ MeCN Ϫ CF3SO3]ϩ. Ϫ 1H NMR
reaction mixture stirred for 18 h at room temperature. The resulting
(CDCl3, Ϫ30°C): δ ϭ 1.24 (t, 6 H, CH3 Et2NCS2), 1.58 (s, 3 H, solid was filtered off and redissolved in 2 ml of CH2Cl2. Addition
CH3 triphos), 1.80 (s, 3 H, MeCN), 2.19 (m, 2 H, CH2 triphos), of 10 ml of diethyl ether led to precipitation of 7 which was dried
2.30 (m, 2 H, CH2 triphos), 2.68 (m, 2 H, CH2 triphos), 3.64 (m, in vacuum. Yield 54.3 mg (67%). Ϫ FAB MS, m/z (%): 900 (26)
1
2 H, CH2 Et2NCS2), 3.84 (m, 2 H, CH2 Et2NCS2), 6.87Ϫ7.38 (m, [M]ϩ, 874 (14) [M Ϫ CN]ϩ, 752 (3) [M Ϫ Et2dtc]ϩ. Ϫ H NMR
30 H, Ph triphos). Ϫ 31P NMR (CDCl3, Ϫ30°C): δ ϭ 26.10 (d, 2
([D6]DMSO): δ ϭ 1.08 (t, 6 H, CH3 Et2NCS2), 1.42 (s, 3 H, CH3
triphos), 2.20Ϫ2.45 (m, 6 H, CH2 triphos), 3.43 (m, 2 H, CH2
P, trans to Et2NCS2), 27.44 (t,
1 P, trans to MeCN). Ϫ
C49H52F3N2O3P3RuS3 ·0.5 C2H5OH (1088.2): calcd. C 55.2, H 5.1, Et2NCS2), 3.67 (m, 2 H, CH2 Et2NCS2), 6.77Ϫ7.79 (m, 30 H, Ph
N 2.6; found C 55.0, H 5.4, N 2.3.
412
triphos). Ϫ 31P NMR ([D6]DMSO): δ ϭ 19.26 (t, 1 P, trans to CN),
Eur. J. Inorg. Chem. 1998, 407Ϫ414

Complexes with the Tripodal Polyphosphane MeC(CH2PPh2)3
FULL PAPER
27.40 (d, 2 P, trans to Et2NCS2). Ϫ IR: ν˜ ϭ 2094 s cmϪ1 (CN). Ϫ 26.60 (t, 1 P), 29.17 (t, 1 P). Ϫ C51H47N2P3RuS2 ·CHCl3 (1065.4):
C47H49N2P3RuS (900.0): calcd. C 62.7, H 5.5, N 3.1; found C 61.8, calcd: C 58.6, H 4.5, N 2.6; found C 58.0, H 4.9, N 2.6.
H 5.9, N 3.1.
[Ru(mpy-κ2N,S)2(triphosO-κ2P) (13): On leaving a reaction
[Ru(Et2NCS2)(H)(triphos)] (8): NaBH4 (11.3 mg, 0.3 mmol) solution of 12 in CHCl3 to stand under air the color changed over
was added to 1 (108.8 mg, 0.1 mmol) in 20 ml at room temperature 3 d from yellow to orange. After 14 d the solution was reduced in
leading to gas formation and lightening of the solution color. After
stirring at room temperature for 18 h the resulting solid was filtered
volume to afford 13 as a yellow solid. C51H47N2OP3RuS2 (962.1):
calcd. C 63.7, H 4.9, N 2.9; found C 62.8, H 5.2, N 2.8. Ϫ FAB
off, washed with ethanol and ethyl ether and dried in vacuum. MS, m/z (%): 962 (84) [M]ϩ, 852 (30) [M Ϫ mpy]ϩ. Ϫ 1H NMR
Yield 66.5 mg (76%). Ϫ FAB MS, m/z (%): 874 (100) [M Ϫ H]ϩ.
(CDCl3) 0.63 (s, 3 H, CH3 triphosO), 2.19 (m, 2 H, CH2 triphosO),
Ϫ 1H NMR (CDCl3): δ ϭ Ϫ5.47 (d, 1 H, 2JPH (trans to H) ϭ 109.4 2.58, 2.79, 2.86, 3.19 (m, 4 H, CH2 triphosO), 6.06 (m, 2 H, mpy),
Hz, 2JPH (trans to S) ϭ 16.6 Hz), 1.24 (t, 6 H, CH3 Et2NCS2), 1.38 6.22, 6.37 (d, 2 H, mpy), 6.76, 6.82 (m, 2 H, mpy) 6.90Ϫ7.70 (m,
(s, 3 H, CH3 triphos), 2.10Ϫ2.23 (m, 6 H, CH2 triphos), 3.61 (m, 32 H, Ph triphosO and mpy). Ϫ 31P NMR (CDCl3) 25.89 (s, 1 P,
2 H, CH2 Et2NCS2), 3.91 (m, 2 H, CH2 Et2NCS2), 6.87Ϫ7.39 (m, PϭO), 42.45 (AB system, 2 P). Ϫ IR: ν ϭ 1200 m (νPO), 568 m
˜
26 H, Ph triphos), 7.74 (s, 4 H, Ph triphos). Ϫ 31P NMR (CDCl3):
δ ϭ 5.29 (m, 1 P, trans to H), 47.10 (d, 2 P, trans to Et2NCS2). Ϫ
cmϪ1 (δPO).
[Ru(mmim-κ2N,S)2(triphosO-κ2P) (14): Hmmim (34.2 mg, 0.3
mmol) was dissolved in 10 ml of MeOH in the presence of 0.3 ml
of 1  NaOH. After addition of 1 (172.0 mg, 0.15 mmol) the solu-
tion was refluxed for 4 h and then left to stand under air for 2 d.
This was followed by filtration and reduction in volume to 1 ml to
afford yellow-brown crystals of 14 at 4°C. Yield 100.2 mg (69%).
IR: ν ϭ 1846 s cmϪ1 (RuH). Ϫ C46H50NP3RuS2 (875.0): calcd. C
˜
63.1, H 5.8, N 1.6; found C 61.9, H 5.8, N 1.4.
[Ru(Et2NCS2-κ2S)(Et2NCS2-κS)(triphos)]
(8):
Na(Et2-
NCS2)·3 H2O (67.0 mg, 0.3 mmol) was added to a solution of 1
(172.0 mg, 0.15 mmol) in 10 ml of MeOH and the reaction mixture
heated at reflux for 3 h. After filtration and reduction in volume Ϫ FAB MS, m/z (%): 968 (25) [M]ϩ, 855 (100) [M Ϫ mmim]ϩ. Ϫ
to 3 ml the resulting solution was left to stand at 4°C to afford a 1H NMR (CDCl3): δ ϭ 0.92 (s, 3 H, CH2 triphosO), 2.94, 2.98 (s,
yellow precipitate of 9 within 24 h. Yield 127.3 mg (83%). Ϫ FAB 6 H, CH3 mmim), 5.93, 6.09, 6.52, 6.61 (d, 4 H, CH mmim), 6.52
MS, m/z (%): 874 (100) [M Ϫ Et2NCS2]ϩ. Ϫ 1H NMR (CDCl3): Ϫ 7.79 (m, 30 H, Ph triphosO). Ϫ 31P NMR (CDCl3): δ ϭ 26.74
δ ϭ 0.86, 1.01 (2 t, 2ϫ6 H, CH3 Et2NCS2), 1.52 (s, 3 H, CH3
(s, 1 P, PϭO), 47.8, 49.9 (AB system, 2 P). Ϫ IR: ν ϭ 571 m cm
˜
Ϫ1
triphos), 2.23, 2.42 (m, 6 H, CH2 triphos), 3.31, 3.54 (m, 8 H, CH2
(δPO). Ϫ C49H49N4OP3RuS2 (968.1): calcd. C 60.8, H 5.1, N
Et2NCS2), 6.60Ϫ7.70 (m, 30 H, Ph triphos). Ϫ 31P NMR (CDCl3): 5.8; found C 61.6, H 4.7, N 6.2.
δ ϭ 19.06 (d, 2 P, trans to Et2NCS2-κ2S), 32.37 (t, 1 P, trans to
X-Ray Structural Analyses Siemens P4 diffractometer, graphite-
Et2NCS2-κS). Ϫ C51H59N2P3RuS4 (1022.3): calcd. C 59.9, H 5.8,
N 2.7; found C 59.8, H 5.0, N 2.6.
˚
monochromated Mo-Kα radiation (λ ϭ 0.71073 A). Semi-empirical
absorption corrections were applied to the intensity data by use of
ψ scans. The structures were solved by a combination of Patterson
[Ru(Et2NCS2-κ2S)2(triphosO-κ2P) (10): Slow crystallization of
9 from an ethanol/acetone solution at room temperature under air and Fourier difference syntheses and refined by full-matrix least
affords 10 in 50% yield over a period of 14 d. Ϫ FAB MS, m/z (%): squares against F for 4, 11, and 14 (SHELXTL PLUS pro-
1038 (100) [M]ϩ, 890 (41) [M Ϫ Et2NCS2]ϩ. Ϫ 1H NMR (CDCl3): grams[27]). Hydrogen atoms were included where possible at calcu-
δ ϭ 0.80Ϫ1.01 (m, 15 H, CH3 of Et2NCS2 and triphosO), lated positions with isotropic temperature factors[28]
2.13Ϫ3.60 (m, 14 H, CH2 of Et2NCS2 and triphosO), 6.80Ϫ7.80
.
4·1/2 CH3OH: C51H46F3N2O3P3RuS3 ·1/2 CH3OH, M ϭ 1098.1,
orthorhombic, space group Pca21 (No. 29), a ϭ 17.3490(3), b ϭ
(m, 30 H, Ph triphosO). Ϫ 31P NMR (CDCl3): δ ϭ 26.86 (s, 1 P,
PϭO) 38.96, 40.38 (2d, 2 P, trans to Et2NCS2). Ϫ IR: ν˜ ϭ 574 m
cmϪ1 (δPO). Ϫ C51H59N2OP3RuS4 (1038.3): calcd. C 59.0, H 5.7,
N 2.7; found C 58.5, H 5.3, N 2.6.
11.315(4), c ϭ 25.440(6) A, V ϭ 4994(2) A3, Z ϭ 4, Dcalc ϭ 1.460
gиcmϪ3, µ ϭ 0.59 mmϪ1. Crystal size 0.42 ϫ 0.48 ϫ 0.49 mm; ω
scan , scan range: 4 Յ 2θ Յ 50°(Ϫ20 Յ h Յ 0, Ϫ13 Յ k Յ 0, 0
Յ l Յ 30), 4963 reflections collected, 4530 symmetry-independent
reflections (Rint ϭ 0.049); max./min. transmission: 0.516/0.470; 613
˚
˚
[Ru(mpym-κ2N,S)(mpym-κS)(triphos) (11): Hmpym (33.6 mg,
0.3 mmol) was dissolved in 10 ml of MeOH in the presence of 0.3
ml of 1  NaOH. After addition of 1 (172.0 mg, 0.15 mmol) and parameters refined; wϪ1 ϭ σ2(Fo) ϩ 0.003 Fo 2, R ϭ 0.040, Rw
ϭ
2
refluxing for 3 h the solvent was removed and the resulting solid
dissolved in a CHCl3/MeOH mixture (2:3). Slow evaporation af-
0.044 for 3896 reflections with Fo > 2σ(Fo2); largest difference
peak: 0.55 eAϪ3. The CF3SO3 anion exhibits rotational disorder
˚
Ϫ
forded yellow crystals of 11. Yield 122.0 mg (74%). Ϫ FAB MS, about the CϪS axis and site occupation factors (s.o.fs) of 0.50 were
m/z (%): 948 (1) [M]ϩ, 837 (100) [M Ϫ mpym]ϩ. Ϫ 1H NMR employed for the F and O atoms of the two observed orientations.
(CDCl3): δ ϭ 1.53 (s, 3 H, CH3 triphos), 2.05 (m, 1 H, CH2
Anisotropic temperature factors were introduced for all nonhydro-
triphos), 2.45 (m, 2 H, CH2 triphos), 2.68 (m, 3 H, CH2 triphos), gen atoms of the cation, the anion S atoms and the C and O atoms
5.62 (s, 1 H, mpym), 6.25 (s, 1 H, mpym) 6.60Ϫ8.00 (m, 34 H,
mpym and Ph triphos). Ϫ 31P NMR (CDCl3): δ ϭ 25.17 (t, 1 P),
26.39 (t, 1 P), 29.05 (t, 1 P). Ϫ C49H45N4P3RuS2 ·MeOH·CHCl3
(1099.4): calcd. C 55.7, H 4.6, N 5.1; found C 56.8, H 4.8, N 5.1.
of a disordered methanol molecule (s.o.fs ϭ 0.5).
11·CHCl3 ·CH3OH: C49H45N4P3RuS2 ·CHCl3 ·CH3OH, M ϭ
1099.4, monoclinic, space group P21/c (No. 14), a ϭ 12.611(3), b ϭ
21.605(4), c ϭ 18.757(4) A, β ϭ 91.01(3)°, V ϭ 5110(2) A3, Z ϭ
4, Dcalc ϭ 1.429 gиcmϪ3, µ ϭ 0.68 mmϪ1. Crystal size 0.32 ϫ 0.39
ϫ 0.42 mm; ω scan , scan range: 4 Յ 2θ Յ 50° (0 Յ h Յ14, Ϫ25
˚
˚
[Ru(mpy-κ2N,S)(mpy-κS)(triphos) (12): The preparation of 12
was performed with Hmpy and 1 under conditions analogous to
those for 11. It was recrystallized within 1 d from a CHCl3 solution Յ k Յ 0, Ϫ22 Յ l Յ 22), 9602 reflections collected, 8898 symmetry-
covered with hexane. Yield 100.7 mg (63%). Ϫ FAB MS, m/z (%): independent reflections (Rint ϭ 0.032); max./min. transmission:
1
2
947 (1) [M]ϩ, 836 (100) [M Ϫ myp]ϩ. Ϫ H NMR (CDCl3): δ ϭ 0.497/0.445; 512 parameters refined; wϪ1 ϭ σ2(Fo) ϩ 0.001 Fo
,
2
1.43 (s, 3 H, CH3 triphos), 2.39 (m, 6 H, CH2 triphos), 5.94 (6, 1
R ϭ 0.061, Rw ϭ 0.058 for 5639 refelctions with Fo > 2σ(Fo2);
H, mpy), 6.15 (d, 1 H, mpy), 6.53 (t, 1 H, mpy), 6.70Ϫ8.00 (m, 35 largest difference peak: 1.13 eAϪ3. Anisotropic temperature factors
˚
H, mpy and Ph triphos). Ϫ 31P NMR (CDCl3): δ ϭ 21.55 (t, 1 P),
were introduced for all nonhydrogen atoms.
Eur. J. Inorg. Chem. 1998, 407Ϫ414
413

C. Landgrafe, W. S. Sheldrick, M. Südfeld
FULL PAPER
[11]
[12]
D. J. Rauscher, E. G. Thaler, J. C. Huffmann, K. G. Caulton,
Organometallics 1991, 10, 2209.
14·CH3OH·1/2 H2O: C49H49N4OP3RuS2 ·CH3OH·1/2 H2O,
M ϭ 1009.1, triclinic, space group P1(No. 2), a ϭ 10.9610(4), b ϭ
¯
C. Bianchini, A. Meli, M. Peruzzini, F. Vizza, A. Albinati, Or-
ganometallics 1990, 9, 2283.
˚
13.944(6), c ϭ 17.590(3) A, α ϭ 76.90(3), β ϭ 88.68(3), γ ϭ
88.94(3)°, V ϭ 2618(2) A3, Z ϭ 2, Dcalc ϭ 1.280 gиcmϪ3, µ ϭ 0.50
G. Kiss, I. T. Horvath, Organometallics 1991, 10, 3798.
˚
[13]
[14]
´
mmϪ1. Crystal size 0.28 ϫ 0.34 ϫ 0.40 mm; ω scan , scan range: 3
Յ 2θ Յ 45° (0 Յ h Յ 11, Ϫ15 Յ k Յ 15, Ϫ18 Յ l Յ 18), 7081
reflections collected, 6659 symmetry-independent reflections
(Rint ϭ 0.050); max./min. transmission: 0.804/0.627; 305 param-
eters refined; wϪ1 ϭ σ2(Fo) ϩ 0.005 Fo2, R ϭ 0.088, Rw ϭ 0.081
for 2803 reflections with Fo2 > 2σ(Fo2); largest difference peak: 1.13
P. Janser, L. M. Venanzi, F. Bachechi, J. Organomet. Chem.
1985, 296, 229.
[15]
E. G. Thaler, K. Folting, K. G. Caulton, J. Am. Chem. Soc.
1990, 112, 2664.
[16]
[17]
[18]
[19]
K. Brandt, W. S. Sheldrick, Chem. Ber. 1996, 129, 1199.
K. Brandt, W. S. Sheldrick, Inorg. Chim. Acta 1997, in press.
W. S. Sheldrick, C. Landgrafe, Inorg. Chim. Acta 1993, 208, 145.
K. Brandt, W. S. Sheldrick, J. Chem. Soc., Dalton Trans 1996,
1237.
eAϪ3. The asymmetric unit contains a disordered water molecule
˚
and two disordered solvent methanols. S.o.fs of 0.5 were employed
for the relevant O and C atoms. Anisotropic temperature factors
were introduced for the Ru, S, P, and O atoms of 15.
[20]
[21]
[22]
C. Landgrafe, W. S. Sheldrick, J. Chem. Soc., Dalton Trans
1994, 1885.
C. Landgrafe, W. S. Sheldrick, J. Chem. Soc., Dalton Trans
1996, 989.
C. A. Ghilardi, F. Laschi, S. Midollini, A. Orlandini, G. Sca-
pacci, P. Zanello, J. Chem. Soc., Dalton Trans 1995, 531.
J. Ott, Dissertation, ETH Zürich, 1986.
[23]
[24]
[1]
C. Bianchini, C. Mealli, A. Meli, M. Peruzzini, F. Zanobini, J.
D. R. Robertson, T. A. Stephenson, J. Organomet. Chem. 1976,
107, C46; D. R. Robertson, T. A. Stephenson, J. Chem. Soc.,
Dalton Trans 1994, 1885.
Am. Chem. Soc. 1988, 8725.
[2]
C. Bianchini, A. Meli, M. Peruzzini, F. Vizza, Y. Fujiwara, T.
[25]
Tintoku, H. Taniguchi, J. Chem. Soc., Chem. Commun. 1988,
C. Bianchini, C. Mealli, A. Meli, M. Sabat, Inorg. Chem. 1984,
23, 2731; C. Bianchini, C. A. Ghilardi, A. Meli, A. Orlandini,
J. Organomet. Chem. 1985, 286, 259.
210.
[3]
C. Bianchini, A. Meli, F. Laschi, J. A. Ramirez, P. Zanello, In-
[26]
[27]
[28]
org. Chem. 1988, 27, 4429.
L. F. Rhodes, C. Sorato, L. M. Venanzi, F. Bachechi, Inorg.
Chem. 1988, 27, 604.
[4]
C. Bianchini, A. Meli, M. Peruzzini, F. Vizza, P. Frediani, J. A.
Ramirez, Organometallics 1990, 9, 226.
G. M. Sheldrick, SHELXTL PLUS programs for use with Sie-
mens X-ray systems, Göttingen, 1990.
[5]
H. A. Mayer, W. C. Kaska, Chem. Rev. 1994, 94, 1239.
[6]
W. O. Siegl, S. J. Lapporte, J. P. Collmann, Inorg. Chem. 1971,
Further details of the crystal structure investigations reported
in this paper have been deposited with the Cambridge Crystal-
lographic Data Centre as supplementary publication no.
CCDC-100819. Copies of the data may be obtained free of
charge on application to the Director, CCDC, 12 Union Road,
Cambridge CB2 1EZ, UK (fax: int. code ϩ44(0)1223/336Ϫ033,
email: deposit@chemcrys.cam.ac.uk)
10, 2158.
[7]
J. Ott, L. M. Venanzi, C. A. Ghilardi, S. Midollini, A. Orlan-
dini, J. Organomet. Chem. 1985, 291, 89.
[8]
G. G. Johnston, M. C. Baird, Organometallics 1989, 8, 1894.
[9]
G. G. Johnston, M. C. Baird, J. Chem. Soc., Chem. Commun.
1989, 1008.
[10]
E. G. Thaler, K. G. Caulton, Organometallics 1990, 9, 1871.
[97267]
414
Eur. J. Inorg. Chem. 1998, 407Ϫ414