diethyldithiophosphate molybdenum complexes: crystal structures
of [Et
4N][Mo(CO)
4{
h
2-S
2P(OEt)
2}] and
[Mo(CH
3CN)(
h
3-C
3H
5)(CO)
2{
h
2-S
2P(OEt)
2}]
Kuang-Hway Yih
a,*, Gene-Hsiang Lee
b, Yu Wang
baDepartment of Applied Cosmetology, Hung Kuang Institute of Technology, Sahlu, Taichung433, Taiwan bDepartment of Chemistry, National Taiwan Uni6ersity, Taipei106, Taiwan
Received 21 April 1999; received in revised form 16 June 1999
Abstract
The air-sensitive dithiophosphate complexes [Et4N][M(CO)4{h2-S2P(OEt)2}] (1, M = Mo; 2, M = W) are accessible by the
reaction of M(CO)4(pip)2(pip = piperidine) (M = Mo, W) with NH4S2P(OEt)2in refluxing acetonitrile in the presence of Et4NBr.
Complex 1 reacts with allyl bromide in CH3CN to give the complex [Mo(CH3CN)(h3-C3H5)(CO)2{h2-S2P(OEt)2}] (3). The
single-crystal structures of complexes 1 and 3 have been determined by X-ray diffraction analyses. Crystal data for 1: space group, C2/c with a = 13.088(7), b = 16.271(4), c = 11.366(7) A, , b=93.88(5)°, V=2414.9(21) A,3, Z = 4. The structure was refined to
R = 0.031 and Rw = 0.031; Crystal data for 3: space group, Pna21with a = 15.979(3), b = 8.613(2), c = 12.720(3) A, , V=1750.6(6)
A,3, Z = 4. The structure was refined to R = 0.026 and Rw = 0.028. Treatment of 3 with piperidine results in the formation of the
complex [Mo(h3-C
3H5)(CO)2{h2-S2P(OEt)2}(C5H10NH)] (4), in which the labile CH3CN ligand was substituted by C5H10NH. The
rotational behaviors of complex 3 and 4 in solution state were detected by variable-temperature1H-NMR spectroscopy. The
mechanism can be described as a trigonal twist, which involves the rotation of the triangular face formed by the nitrogen ligand and the two sulfur atoms relative to the face formed by the allyl and the two carbonyl groups. The 16-electron dithiocarbamate complex [Mo(h3-C
3H5)(CO)2(h2-S2CNC5H10)] (5) is produced by S2P(OEt)2− ligand replacement of 4 with C5H10NC(S)SH or the
insertion reaction of CS2into the MoN bond of 4 with releasing of the (EtO)2P(S)SH ligand. © 1999 Elsevier Science S.A. All
rights reserved.
Keywords:Molybdenum; Diethyldithiophosphato ligand; Trigonal twist; Carbon disulfide; Insertion reaction
1. Introduction
The anionic dithiophosphate ligands, S2P(OR)2−
(R = alkyl), have proven to be versatile, and can bind as a unidentate [1], chelating [2], or bridging [3] ligand to a wide range of transition metals. These ligands are of interest, in part, due to their use as catalyst additives [4], sequestering agents [5] and isolation of the cuban-like cluster [6]. Although many simple M{S2P(OEt)2}n
species have been prepared [7], fewer organometallic dithiophosphate molybdenum complexes except Cp-Mo(CO)2{S2P(OPr
i
)2} [8a], Mo(CO)2{S2P(OEt)2
}-(NCMe)(SnRCl2) [9a], Mo(CO)2{S2P(OEt)2}(S2CPCy3
)-(SnPhCl2) [9b] and Mo2(h3-C3H5)2(CO)4{S2P(OEt)2}2
-(m-NH2NH2) [9c] have been characterized and only rarely subjected to crystallographic study.
Complexes of the type [MoL(h3-C
3H5)(CO)2A] (A:
pyrazolylborate or b-diketonate ligand, L: neutral monodentate ligand) have been known for more than 15 years. Notably, the solution rotational behavior [10] and structures [11] of these compounds containing the nitrogen, phosphine, and oxygen bidentate ligands have been studied clearly but no detailed information has been presented on the sulfur-containing bidentate lig-and such as (EtO)2PS2− in this rotating system.
In the context of our previous studies on transition metal complexes containing the anionic sulfur ligands,
* Corresponding author. Fax: + 886-4-6321046.
0022-328X/99/$ - see front matter © 1999 Elsevier Science S.A. All rights reserved. PII: S 0 0 2 2 - 3 2 8 X ( 9 9 ) 0 0 3 5 7 - 5
Scheme 1.
13C{1H}-NMR spectra of 1 and 2 are attributed to the
carbon atoms of the two carbonyl groups.
To demonstrate the structure of the first Group VIB(0) dithiophosphate compound, complex 1 was confirmed by single-crystal X-ray diffraction study. The
ORTEP diagram with atom labels is shown in Fig. 1.
C5H10NCS2−, Ph2PCS2− and Ph2PC(NPh)S− [12], and
in view of above-mentioned interesting results, we ex-tended our investigation to a study of the diethyldithio-phosphato, (EtO)2PS2−, ligand. In this paper, we
describe the synthesis, structures and the rotational behavior of theh3-allyl molybdenum complex involving
the diethyldithiophosphato, (EtO)2PS2−, ligand.
2. Results and discussion
2.1. Synthesis of anionic dithiophosphate complexes
[Et4N][Mo(CO)4{h2-S2P(OEt)2}] (1) and
[Et4N][W(CO)4{h2-S2P(OEt)2}] (2)
The air-sensitive compounds of the type
[Cat][Mo(CO)4LL] (Cat=Na, K, NH4;
LL=dithio-carbamto, xanthato, dithiophosphato) were prepared by heating (60 – 65°C) Mo(CO)6 [8b] or M(CO)4(pip)2
(M = Mo, W) [16] with ligand salt in degassed DMSO or CH3CN, respectively. The [Et4N][Mo(CO)4{h2
-S2P(OEt)2}] complex has been prepared for use in the
95Mo-NMR experiment [8a] and these complexes were
so unstable that some reports described them as non-isolable [8b]. We used the dithiophosphato ligand NH4S2P(OEt)2 with M(CO)4(pip)2 (M = Mo, W) in
refluxing CH3CN in the presence of Et4NBr to lead to
the formation of the clean and high-yield dithiophos-phate complexes [Et4N][M(CO)4{h2-S2P(OEt)2}] (1,
M = Mo; 2, M = W) (Scheme 1). The two yellow crys-talline, very air-sensitive products 1 and 2 were ob-tained by recrystallization from CH2Cl2– n-hexane in 78
and 65% yield, respectively. Complexes 1 and 2 are very soluble even in diethyl ether but slightly soluble in
n-hexane. In the FAB mass spectra, two base peaks
with the typical Mo and W isotope distribution are respectively in agreement with the [M++ Et
4NCO]
molecular masses of 1 and 2. The IR spectra of 1 and 2, respectively show two sets of four terminal carbonyl-stretching bands that reveal a C26(2A1+ B1+ B2)
sym-metry of carbonyl ligands about the metal center. In the
31P{1H}-NMR spectra of 1 and 2, two singlets at high
field relative to the free NH4S2P(OEt)2 ligand indicate
the coordination of the dithiophosphato ligand. The
1H-NMR spectra comprise the proton resonances of
S2P(OEt)2− and Et4N+ with the integration ratio
6:4:12:8 of 1 and 2. Two singlets at lowest field in the
Fig. 1. ORTEP diagram of the anionic complex [Mo(CO)4{h2
-S2P(OEt)2}]− (1).
Fig. 2.ORTEPdiagram of complex [Mo(CH3CN)(h3-C3H5)(CO)2{h2
MoS(1)S(1a) and MoC(4)C(4a). The structure of the anion of 1 possesses a C2 crystallographic axis through
Mo and P atoms and thus becomes C26 symmetry.
Complex 1 possesses two groups of MoCO bond distances of 1.924(4) and 2.015(4) A, due to the trans effect of the carbonyl groups. The MoS bond distance of 1 (2.622(1) A, ) is longer than those of complex [Et4N][Mo(CO)4(h2-S2CNEt2)] [17] (average value of
MoS bonds, 2.593(1) A,) and [Et4N][Mo(CO)4(h2
-S2CNC5H10)] (2.594(1) A, ) [12f]. It reflects the S2CNEt2−
ligand with morep-acceptor ability than the S2P(OEt)2−
ligand. In fact, the S2P(OEt)2− ligand can be replaced
by the S2CNC5H10− ligand (described below). Compared
with the Mo(0)S2P(OEt)2 complex and Mo(III, V)S2P(OR)2 complexes, the MoS distance of 1
(2.622(1) A, ) is significantly longer than those observed in the dithiophosphato complexes Mo{S2P(OMe)2}3
(2.501 – 2.520(2) A, ) [7b] and [{MoOS2P(OPri)2}2OS]
(2.334, 2.370(4) A, ) [18] in a higher oxidation state. It seems that the higher the Mo oxidation state is, the shorter the MoS bond distance becomes.
2.2. Reaction of complex
[Et4N][Mo(CO)4{h2-S
2P(OEt)2}] (1) with allyl bromide Treatment of [Et4N][Mo(CO)4{h2-S
2P(OEt)2}] (1)
with allyl bromide in CH3CN afforded the acetonitrile solvate complex [Mo(CH3CN)(h3-C3H5)(CO)2{h2
-S2P(OEt)2}] (3) in 82% isolate yield. Miguel and
co-workers have also described the preparation of complex
3 and several molybdenum – tin, and m-NH2NH2
com-plexes [9] containing dithiophosphato ligand. All spec-troscopic data for 3 are consistent with the literature. However, solution IR spectra show the two carbonyls in equal intensity; this observation indicates that the two carbonyls are mutually cis. From an AM2X2
pat-tern of the allyl group in the1H-NMR spectra and one
equivalent resonance of the terminal carbon of the allyl group and one resonance of carbonyl group in the
13C{1H}-NMR spectra, it reveals the bidentate ligand
and the two carbonyls lie in a horizontal plane, whereas the allyl group and the CH3CN ligand lie in a trans
positions above and below the plane, respectively (Scheme 1). Because the mentioned structure is incom-patible with the report by Miguel and the correspond-ing acetonitrile allyl dithiophosphato structure still remains unknown, we have performed an X-ray diffrac-tion study of 3 to elucidate the solid-state structure. An
ORTEPplot of 3 is shown in Fig. 2. Table 5 shows the
Fig. 3. Variable-temperature1H-NMR spectra of 3 in acetone-d 6.
selected bond distances and bond angles of 3. The coordination geometry around the molybdenum atom is approximately an octahedron with the two dithio-phosphato sulfur atoms, acetonitrile, two carbonyls and the allyl group occupying the six coordination sites. The structure confirms an unequivalent allyl group. One of the sulfur atoms of dithiophosphato is trans to the allyl: S(1)MoC(10), 160.7(2)°, while the other is
trans to one carbonyl: S(2)MoC(8), 167.4(3)°. The
remaining carbonyl is trans to the nitrogen atom of the acetonitrile: C(7)MoN, 170.4(2)°. The SMoS angle of 75.97(7)° in 3 is similar to 75.95(5)° in 1 within experimental errors. The MoC(9), C(10) and C(11) bond distances are 2.297(8), 2.226(7) and 2.339(6) A, , respectively. The MoS(1) distance of 2.565(2) A, (trans
Scheme 2.
to allyl) is slightly shorter than MoS(2) of 2.638(2) A, (trans to CO) because of the greater trans effect induced by the CO group than the allyl group.
In order to resolve this apparent anomaly between the solution spectroscopy and solid-state structure, the
variable-temperature 1H-NMR experiments were
undertaken. By variable-temperature1H-NMR spectra,
complex 3 in solution exhibits fluxional behavior, and the dynamic process has been examined. As depicted in Fig. 3, an AM2X2 pattern is observed for the allyl protons, and a single resonance for the methyl protons
of the acetonitrile group. However, on cooling
(CD3)2CO solutions of 3, the proton signals initially
broaden and below 245 K the methyl resonance of CH3CN and the syn- and anti-proton signals of the
allyl moiety each begin to separate into two
components. Below 233 K, 1H-NMR data are in
accordance with the two possible structures of 3. A ratio of the unsymmetry and symmetry components (1.2:1) at 213 K in (CD3)2CO was derived from
intensity measurements. The mechanism can be
described as a trigonal twist, which involves the rotation of the triangular face formed by the CH3CN and the two sulfur atoms relative to the face formed by the allyl and the two carbonyl groups. The rotation mechanism has been previously described for the trigonal twist behavior of [Mo(pd)(h3-C
3H5)(CO)2(py)]
[11] and other related complexes [10]. Line-shaped analysis calculated from variable-temperature1H-NMR
spectra of 3 yields a value of 11.690.2 kcal mol− 1for
DG‡. Compared with other rearrangement complexes,
the activation energy of 3 is almost the same as that of complex Mo(h3-C
3H5)(CO)2(dppm)I (11.2 kcal mol− 1)
[10d] and is smaller than that of complex
[Mo(pd)(h3-C
3H5)(CO)2(py)] (14.3 kcal mol− 1) [11b].
Attempts to prepare a similar product from the reaction of 2 with allyl bromide were unsuccessful. No reaction occurred under the similar reaction conditions and complex 2 decomposed in refluxing conditions.
2.3. Synthesis of complex [Mo(h3-C
3H5)(CO)2
-{h2-S
2P(OEt)2}(C5H10NH)] (4) Complex [Mo(h3-C
3H5)(CO)2{h2-S2P(OEt)2}(C5H10
-NH)] (4) was prepared by the reaction of 3 with C5H10NH at ambient temperature (Scheme 2). The yellow compound 4 is slightly air-sensitive, soluble in polar solvent, and slightly soluble in n-hexane. The FAB mass spectrum of 4 shows a parent peak corre-sponding to the [M+] molecular mass. Similar
spectro-scopic phenomena of the carbonyl group and allyl moiety in IR and1H-, 13C{1H}-NMR spectra led us to
believe that complex 4 contains the same solution rota-tional behavior as 3. To confirm the result, the variable-temperature 1H-NMR experiments of 4 were carried
out. TheDG‡ value calculated from line-shape analysis
of the variable-temperature 1H-NMR was 12.690.2
kcal mol− 1 for 4. The large activation energy of 4
compared with 3 is due to the more steric hindrance of the C5H10NH ligand than CH3CN. In fact, this value is essentially independent of the nature of the dithiophos-phato ligand, increases with increase in the size of the neutral monodentate ligand, and is greater for the substituted allyl than for the allyl complexes. Notably, the dissociation mechanism [11] of the C5H10NH ligand
was neglected because when the temperature was in-creased to 330 K,1H-NMR resolved no free C
5H10NH
Orthorhombic Monoclinic Crystal system 0.50×0.50×0.40 Crystal size (mm) 0.60×0.50×0.50 Pna21 C2/c Space group 13.008(7) a (A, ) 15.979(3) 8.613(2) 16.271(4) b (A, ) 11.366(7) c (A, ) 12.720(3) b (°) 93.88(5) 1750.6(6) 2414.9(21) V (A,3) 4 Z 4 1.591 1.440 Dcalc(g cm−3) 1.57 m (Mo–Ka), mm−1 1.06 842 1074 F(000) 50.0 2umax 50.0 Index ranges (h,k,l) −1515, 019, 018, 010, 0 15 013 Reflections collected 2121 1618 Observed data [I\2s(I)] 1703 1364 No. of parameters 125 181 0.026 0.031 Ra 0.031 Rwb 0.028 0.588, 0.652 0.533, 0.565 Max./min. transmission 38 No. of atoms 30 1.48 1.13 Quality-of-fitc D(D-map) max./min. −0.340, 0.300 −0.320, 0.220 (e A,−3) aR =S F o − Fc /S Fo . b Rw = [Sv( Fo − Fc ) 2]1/2, wherev=1/s2( F o ). cQuality-of-fit = [Sv( F o − Fc )2/(Nreflections−Nparameters)]1/2. C3H5)(CO)2(h2-S2CNR2)] [20]. The 13C{1H}-NMR
spectrum of 5 reveals two singlets at lowest field, which are assigned to the carbon atoms of the carbon disulfide and the terminal carbonyl groups, respectively. Com-plex 5 can also be obtained by the reaction of comCom-plex [Mo(h3-C
3H5)(CO)2{h2-S2P(OEt)2}(C5H10NH)] (4) with
carbon disulfide (Scheme 2). The CS2insertion reaction
into the MN bond (M=Cr, Mo, W) promoted by the abstraction of a proton on the nitrogen atom of the piperidine ligand by n
BuLi to form theh2
-dithiocarba-mate ligand has been reported by us [12f]. The reaction of 4 and CS2 is believed to be induced by the stronger p-acceptor ability of C5H10NCS2− ligand, by insertion
of CS2 into the MoN bond of 4 to give dithiocarba-mate complex 5 with release of the (EtO)2P(S)SH
ligand.
2.5. Conclusions
We have investigated the synthesis and structure of the air-sensitive anionic dithiophosphate tetracarbonyl Mo(0) and W(0) complexes 1 and 2, respectively. The variable-temperature 1H-NMR experiments were used
to confirm the trigonal twist behavior of both the stereochemical non-rigidity of [Mo(CH3CN)(h3
-C3H5)(CO)2{h2-S
2P(OEt)2}] (3) and [Mo(h3
-C3H5)(CO)2{h2-S
2P(OEt)2}(C5H10NH)] (4) at room
temperature. The greater p-acceptor ability of
S2CNC5H10− than S2P(OEt)2− induced the insertion
re-action of CS2 into the MoN bond of 4 to yield the
16-electron complex [Mo(h3-C
3H5)(CO)2(h2-S2
CN-C5H10)] (5).
3. Experimental
3.1. Materials
All manipulations were performed under nitrogen using vacuum-line, drybox, and standard Schlenk tech-niques. NMR spectra were recorded on a Bruker AM-200, or on an AM-300 WB FT-NMR spectrometer and are reported in units of d (ppm) with residual protons in the solvent as an internal standard (CDCl3, d 7.24;
CD3CN, d 1.93; C6D6, d 7.15; C2D6CO, d 2.04). IR
spectra were measured on a Perkin – Elmer 983 instru-ment and were referenced to a polystyrene standard, using cells equipped with calcium fluoride windows. Mass spectra were recorded on a Jeol SX-102A spec-trometer. Solvents were dried and deoxygenated by Miguel and co-workers have reported the reactions
of 3 with uni- and bidentate nitrogen ligands. Other reactions of 3 with diphos and phenylacetylene will be discussed in a forthcoming paper [19].
2.4. Preparation of the 16-electron dithiocarbamate
complex [Mo(h3-C
3H5)(CO)2(h2-S2CNC5H10)] (5) The neutral, 16-electron dithiocarbamate complexes [Mo(h3-C
3H5)(CO)2(h2-S2CNR2)] [20] were prepared
directly by replacement of CH3CN and Br of complex
Mo(CH3CN)2(h3-C3H5)(CO)2Br by dithiocarbamate
ligands. Other methods for synthesis of the dithiocarba-mate complexes have been reported by insertion of carbon disulfide into the metal – nitrogen bond [12f,21]. We used complex [Mo(CH3CN)(h3-C
3H5)(CO)2{h2
-S2P(OEt)2}] (3) with C5H10NC(S)SH in CH2Cl2 to lead
to the formation of the clean and high-yield 16-electron dithiocarbamate complex [Mo(h3-C
3H5)(CO)2(h2
-S2CNC5H10)] (5) with release of (EtO)2P(S)SH ligand
(Scheme 2). The yellow – orange crystalline product 5 was slightly air-sensitive, insoluble in CH2Cl2, CH3CN
and only slightly soluble in DMSO. Because of the low solubility, we cannot obtain a good-quality single
crys-refluxing over the appropriate reagents before use. n-Hexane, diethyl ether, THF and benzene were distilled from sodium-benzophenone. Acetonitrile and dichloro-methane were distilled from calcium hydride, and methanol from magnesium. All other solvents and reagents were of reagent grade and were used as re-ceived. Metal carbonyls, allyl bromide and NH4S2
P-(OEt)2were purchased from Strem, Merck and Janssen,
respectively. The compounds M(CO)4(C5H10NH)2
(M = Mo, W) [13] were prepared according to the literature methods. Elemental analyses and X-ray dif-fraction studies were carried out at the Regional Center of Analytical Instrument located at the National Tai-wan University.
3.2. [Tetraethylammonium][(tetracarbonyl)(h2
-diethyldithiophosphato)molybdenum(0)] (1)
MeCN (40 ml) was added to a flask (100 ml) contain-ing NH4S2P(OEt)2 (0.406 g, 2.0 mmol), Et4NBr (0.535 g, 2.5 mmol) and Mo(CO)4(C5H10NH)2 (0.756 g, 2.0
mmol). The solution was refluxed for 10 min, and an IR spectrum indicated completion of the reaction. After cooling the solution and removal of the solvent in vacuo, the residue was abstracted with diethyl ether (3 × 20 ml). Upon cooling below 0°C, yellow solids of 1 were formed which were isolated by filtration (G4), washed with n-hexane (2 × 10 ml) and subsequently dried under vacuum yielding 0.82 g (78%) of 1. Further purification was accomplished by recrystallization from 1:10 CH2Cl2– n-hexane. IR (KBr) n(CO) 1999(m), 1861(vs), 1840(vs), 1801(vs) cm− 1. 31P{1H}-NMR (80 MHz, C2D6CO, 298 K): d 104.6.1H-NMR (200 MHz, C2D6CO, 298 K): d 1.25 (t, J(HH) 7.4 Hz, 6H, OCH2CH3), 1.38 (tt, 3J(NH) 1.9, J(HH) 7.3 Hz, 12H, NCH2CH3), 3.47 (q, J(HH) 7.3 Hz, 8H, NCH2), 4.03 (dq, 3J(PH) 9.5, J(HH) 7.4 Hz, 4H, OCH 2). 13C{1 H}-NMR (50 MHz, CDCl3, 298 K): d 7.5 (s, NCH2CH3), 15.8 (s, OCH2CH3), 52.6 (s, NCH2), 62.3 (s, OCH2),
206.5 (s, cis-CO), 222.1 (s, trans-CO). MS (FAB, NBA)
m/z 627 [M++ Et
4NCO]. Anal. Calc. for
C16H30NO6PS2Mo: C, 36.71; H, 5.78; N, 2.68. Found:
C, 36.90; H, 5.60; N, 2.50%.
3.3. [Tetraethylammonium][(tetracarbonyl)(h2
-diethyl-dithiophosphato)tungsten(0)] (2)
NH4S2P(OEt)2 (0.406 g, 2.0 mmol) and Et4NBr (0.535 g, 2.5 mmol) were dissolved in MeCN (20 ml)
and the solution was added to a solution of
W(CO)4(C5H10NH)2 (0.932 g, 2.0 mmol) in MeCN (40
ml). The solution was refluxed for 30 min, and an IR spectrum indicated completion of the reaction. After cooling the solution and removal of the solvent in vacuo, the residue was abstracted with diethyl ether (3 × 20 ml). Upon cooling below − 18°C for 1 day,
Table 2
Atomic parameters x, y, z, and Beqfor important atoms of 1 a x y z Beq Atom Mo 0 0.31337(3) 1/4 4.228(19) 5.69(5) 0.15031(9) 0.18635(7) S(1) 0.08208(9) 4.95(7) 1/4 P(1) 0 0.11565(9) 0.05025(16) 0.1773(3) −0.06698(22) 6.28(13) O(1) 0.0919(4) 0.0764(3) 7.7(3) C(1) −0.1465(4) 0.0225(3) −0.0051(5) −0.1553(5) 9.5(3) C(2) 0.3177(3) 0.1235(4) C(3) −0.1154(3) 5.91(20) 9.92(21) 0.0522(3) O(3) −0.1797(3) 0.3238(3) 0.0679(4) 0.3992(3) 0.1687(4) 6.63(24) C(4) 0.1065(4) 0.45284(22) O(4) 0.1221(3) 10.46(24)
aEstimated S.D. values are in parentheses.
Table 3
Selected interatomic distances (A, ) and angles (°) for 1 MoS(1) 2.6219(13) OC(1) 1.439(5) C(1)C(2) 1.408(7) 2.6219(13) MoS(1a) MoC(3) 2.015(4) C(3)O(3) 1.132(5) MoC(3a) 2.015(4) C(4)O(4) 1.155(5) 1.924(4) MoC(4) MoC(4a) 1.924(4) 1.9815(16) S(1)P(1) 1.9815(16) P(1)S(1a) 1.576(3) P(1)O(1a) P(1)O(1) 1.576(3) S(1)MoS(a) 75.95(5) S(1)P(1)O(1) 113.33(12) 91.64(12) S(1)PO(1a) S(1)MoC(3) 112.81(12) S(1)MoC(3a) 91.55(14) SaP(1)O(1) 112.81(12) S(1)MoC(4) 98.55(15) SaP(1)O(1a) 113.33(12) S(1)MoC(4a) 174.50(14) O(1)P(1)O(1a) 95.08(16)
P(1)O(1)C(1) 120.3(3) 91.55(14)
S(1a)MoC(3)
S(1a)MoC(3a) 91.64(12) O(1)C(1)C(2) 111.2(4) 177.0(4) MoC(3)O(3) S(1a)MoC(4) 174.50(14) MoC(4)O(4) 177.5(4) S(1a)MoC(4a) 98.55(15) C(3)MoC(4) 89.84(20) C(3)MoC(3a) 175.95(18) 88.23(19)
C(3)MoC(4a) C(3a)MoC(4) 88.23(19) C(3a)MoC(4a) 88.84(20) C(4)MoC(4a) 86.94(20) 87.51(6) S(1)P(1)S(1a) 109.02(9) MoS(1)P(1)
yellow solids were formed, which were isolated by filtration (G4), washed with cold (0°C) n-hexane (2 × 10 ml) and subsequently dried under vacuum to yield 0.79 g (65%) of 2. Further purification was accom-plished by recrystallization from 1:20 CH2Cl2–
n-hex-ane. IR (KBr) n(CO) 1993(m), 1841(vs), 1833(vs), 1798(vs) cm− 1.31P{1H}-NMR (80 MHz, C 2D6CO, 298 K): d 99.0. 1H-NMR (200 MHz, CD 3CN, 298 K): d 1.20 (tt, 3J(NH) 1.9, J(HH) 7.3 Hz, 12H, NCH 2CH3), 1.28 (t, J(HH) 7.4 Hz, 6H, OCH2CH3), 3.16 (q, J(HH) 7.3 Hz, 8H, NCH2), 4.06 (dq, 3J(PH) 9.5, J(HH) 7.4 Hz, 4H, OCH2). 13C{1H}-NMR (50 MHz, CDCl3, 298 K): d 7.6 (s, NCH2CH3), 16.2 (s, OCH2CH3), 52.9 (s, NCH2), 63.3 (s, OCH2), 203.9 (s, cis-CO), 212.0 (s,
trans-CO). MS (FAB, NBA) m/z 713 [M++
Et4NCO]. Anal. Calc. for C16H30NO6PS2W: C, 31.43;
0.62411(12) 0.6547(3) S(2) 0.83715(16) 4.76(9) 0.71659(10) 0.79941(23) P(1) 0.80612(18) 4.60(8) 0.7102(3) 0.9598(6) O(1) 0.8659(4) 6.5(3) 0.8514(9) 1.0631(13) 0.6437(6) 9.4(6) C(1) 0.6505(6) 1.2053(11) C(2) 0.9038(9) 8.4(6) 0.8021(3) 0.7495(6) O(2) 0.8605(4) 6.5(3) 0.8384(6) 0.6019(12) C(3) 0.8388(10) 8.5(6) 0.8982(11) 0.5784(12) 0.9113(6) 10.1(6) C(4) N(1) 0.7014(3) 0.4617(5) 0.6369(6) 4.5(3) C(5) 0.7539(4) 0.3747(7) 0.6325(8) 4.5(4) C(6) 0.8233(4) 0.2643(8) 0.6333(9) 6.3(3) C(7) 0.5258(4) 0.8198(7) 0.6234(7) 5.0(3) O(7) 0.4835(3) 0.9288(6) 0.6156(5) 7.1(3) C(8) 0.5997(5) 0.6648(10) 0.4809(7) 5.9(4) O(8) 0.5987(5) 0.6863(9) 0.3907(5) 9.5(4) 7.9(5) 0.5546(9) 0.4324(11) C(9) 0.5343(6) C(10) 0.5129(5) 0.4421(9) 0.6603(7) 5.7(4) 0.4634(4) 0.5717(9) 0.6838(6) 6.1(4) C(11)
aEstimated S.D. values are in parentheses.
MoC(8) 1.939(9) C(3)C(4) 1.403(13) 1.126(7) 2.297(8) N(1)C(5) MoC(9) 2.226(7) MoC(10) C(5)C(6) 1.461(8) 2.339(6) MoC(11) C(7)O(7) 1.160(8) 1.976(3) S(l)P(1) C(8)O(8) 1.162(11) S(2)P(1) 1.973(3) C(9)C(10) 1.390(15) 1.581(5) P(1)O(1) C(10)C(11) 1.400(12) 75.97(7) S(1)MoS(2) C(9)MoC(10) 35.7(4) 82.09(12) C(9)MoC(11) S(1)MoN(1) 60.3(3) 88.70(18) S(1)MoC(7) C(10)MoC(11) 35.6(3) S(1)MoC(8) 91.5(3) MoS(1)P(1) 88.82(8) S(1)MoC(9) 151.5(3) MoS(2)P(1) 86.84(10) S(1)P(1)S(2) 108.36(12) 160.73(20) S(1)MoC(10) 148.19(20) S(1)MoC(11) S(1)P(1)O(1) 112.05(24) 83.94(20) S(2)MoN(1) S(1)P(1)O(2) 114.64(24) 96.6(3) S(2)P(1)O(1) S(2)MoC(7) 114.05(22) S(2)MoC(8) 167.4(3) S(2)P(1)O(2) 112.68(24) O(1)P(1)O(2) 94.7(3) 121.9(3) S(2)MoC(9) P(1)O(1)C(1) 122.8(5) S(2)MoC(10) 88.37(23) 115.7(8) O(1)C(1)C(2) S(2)MoC(11) 82.94(19) 170.36(21) P(1)O(2)C(3) N(1)MoC(7) 120.5(5) 95.3(3) O(2)C(3)C(4) N(1)MoC(8) 111.3(8) 78.5(3) N(1)MoC(9) MoN(1)C(5) 175.4(7) 85.20(24) N(1)MoC(10) N(1)C(5)C(6) 176.5(10) 119.36(23) N(1)MoC(11) MoC(7)O(7) 177.9(6) C(7)MoC(8) 82.0(3) MoC(8)O(8) 176.7(7) MoC(9)C(10) 69.3(4) 109.0(3) C(7)MoC(9) C(7)MoC(10) 104.4(3) MoC(10)C(9) 74.9(5) C(7)MoC(11) 70.2(3) MoC(10)C(11) 76.6(4) 69.9(4) C(8)MoC(9) C(9)C(10)C(11) 113.2(8) 67.8(4) 104.1(3) MoC(11)C(10) C(8)MoC(10) C(8)MoC(11) 108.1(3) 3.4. (Acetonitrile)(h3-allyl)(dicarbonyl)(h2
-diethyl-dithiophosphato)molybdenum(II) (3)
An aliquot of C3H5Br (0.1 ml, 1.2 mmol) was added
to a flask containing a solution of 1 (0.523 g, 1.0 mmol) in MeCN (20 ml). After stirring for 10 min, the mixture was cooled and the solution was removed in vacuo. The residue was redissolved in CH2Cl2 (5 ml).
n-Hexane (20 ml) was added to the solution and a
yellow – orange precipitate was formed. The precipitate was collected by filtration (G4) washed with n-hexane (2 × 10 ml) and then dried in vacuo yielding 0.34 g (82%) of 3. Recrystallization using a mixture of cold 20:1 MeOH – CH2Cl2 gave the yellow – orange
crys-talline product [Mo-(CH3CN)(h3-C3H5)(CO)2{h2-S2
P-(OEt)2}] (3). IR (KBr) n(CO) 1926(vs), 1841(vs) cm− 1. 31P{1H}-NMR (80 MHz, CD 3CN, 298 K): d 100.9. 1H-NMR (200 MHz, CD 3CN, 298 K): d 1.26 (t, 3J(HH) 7.4 Hz, 6H, OCH 2CH3), 1.28 (d, J(HH) 10.0 Hz, 2H, Hanti of allyl), 1.95 (s, 3H, CH3CN), 3.29 (d, J(HH) 5.5 Hz, 2H, Hsyn of allyl), 4.03 (dq, 3J(PH) 9.5, J(HH) 7.4 Hz, 4H, OCH2), 4.29 (m, 1H, CH of allyl).13C{1H}-NMR (50 MHz, CD 3CN, 298 K):d 3.3 (s, CH3CN), 15.8 (s, OCH2CH3), 55.7 (s, CHCH2), 62.9 (s, OCH2), 71.5 (s, CH2CH), 119.5 (s, CH3CN),
225.0 (s, CO). MS (FAB, NBA): m/z 421 [M+], 380
[M+− CH
3CN], 339 [M+− CH3CNC3H5], 311
[M+− CH
3CNC3H5CO], 283 [M+− CH3CN
C3H52CO]. Anal. Calc. for C11H18NO4PS2Mo: C,
31.51; H, 4.33; N, 3.34. Found: C, 31.70; H, 4.21; N, 3.25%.
3.5. (h3-Allyl)(dicarbonyl)(h2-diethyldithiophosphato
)-(piperidine)molybdenum(II) (4)
A solution of [Mo(CH3CN)(h3-C3H5)(CO)2{h2
-S2P(OEt)2}] (3) (0.419 g, 1.0 mmol) in CH2Cl2 (20 ml) was treated with C5H10NH (0.1 ml, 1.2 mmol) at
ambi-ent temperature. Instantly, the reaction mixture turned yellow. After 10 min of stirring, the solution was dried in vacuo. Subsequently, n-hexane (40 ml) was added to the solution and a yellow precipitate was formed. The precipitate was collected by filtration (G4) and dried in vacuo to yield 0.35 g (76%) of 4. IR (KBr) n(CO) 1929(vs), 1833(vs) cm− 1. 31P{1H}-NMR (80 MHz, CDCl3, 298 K): d 110.4. 1H-NMR (200 MHz, CDCl3, 298 K): d 1.12 (d, J(HH) 9.4 Hz, 2H, Hanti of allyl), 1.33 (t, 3J(HH) 7.4 Hz, 6H, OCH 2CH3), 1.77 (m, 6H, NCH2CH2CH2) 3.25 (d, J(HH) 6.6 Hz, 2H, Hsyn of allyl), 3.53 (m, 4H, NCH2), 3.90 (m, 1H, CH of allyl), 4.08 (dq, 3J(PH) 9.5, J(HH) 7.4 Hz, 4H, OCH 2). 13C{1H}-NMR (50 MHz, CDCl 3, 298 K): d 16.0 (s,
OCH2CH3), 23.8 (s, NCH2CH2CH2), 28.9 (s,
NCH2CH2), 53.0 (s, NCH2), 57.0 (s, CHCH2), 63.0 (s,
OCH2), 71.4 (s, CH2CH), 227.0 (s, CO). MS (FAB, NBA): m/z 464 [M+], 436 [M+− CO], 408 [M+−
2CO]. Anal. Calc. for C14H26NO4PS2Mo: C, 36.28; H, 5.66; N, 3.02. Found: C, 36.25; H, 5.61; N, 3.12%.
3.6. (h3-Allyl)(dicarbonyl)(h2
-piperidine-N-dithiocarbamato)molybdenum(II) (5) 3.6.1. Method A
A solution of C5H10NC(S)SH (0.161 g, 1.0 mmol) in
MeOH (5 ml) was added to a flask containing 3 (0.419 g, 1.0 mmol) in CH2Cl2 (20 ml). The solution was
stirred for 1 min and a yellow – orange precipitate formed. The precipitate was collected by filtration (G4), washed with n-hexane (2 × 10 ml) and then dried in vacuo to yield 0.35 g (99%) of 5. IR (KBr) n(CO) 1945(vs), 1917(vs), 1865(vs), 1847(vs) cm− 1. 1H-NMR (200 MHz, DMSO-d6, 298 K):d 1.17 (d, J(HH) 9.8 Hz, 2H, Hanti of allyl), 1.50 (m, 6H, NCH2CH2CH2), 3.13 (d, J(HH) 6.4 Hz, 2H, Hsyn of allyl), 3.83 (m, 4H, NCH2), 4.00 (m, 1H, CH of allyl). 13C{1H}-NMR (50 MHz, DMSO-d6, 298 K): d 23.7 (s, NCH2CH2CH2), 25.7 (s, NCH2CH2), 48.0 (s, NCH2), 58.1 (s, CHCH2), 74.7 (s, CH2CH), 204.2 (s, CS2), 230.1 (s, CO). MS
(EI, 20 eV): m/z 355 [M+], 327 [M+− CO], 299
[M+− 2CO]. Anal. Calc. for C
11H15NO2S2Mo: C,
37.39; H, 4.28; N, 3.97. Found: C, 37.52; H, 4.42; N, 3.75%.
3.6.2. Method B
An aliquot of CS2(0.1 ml, 1.6 mmol) was added to a solution of 4 (0.463 g, 1.0 mmol) in CH2Cl2 (20 ml). Instantly, the reaction was completed. A yellow – orange precipitate was formed which was isolated by filtration (G4), and was washed with n-hexane (2 × 10 ml) and subsequently dried under vacuum to yield 0.33 g (94%) of 5.
3.7. X-ray crystallography
A single crystal of 1 suitable for X-ray diffraction analysis was grown by recrystallization from 20:1 n-hexane – CH2Cl2. The diffraction data were collected at room temperature on an Enraf – Nonius CAD4 diffrac-tometer equipped with graphite-monochromated Mo – Ka (l=0.71073 A,) radiation. The raw intensity data were converted to structure factor amplitudes and their estimated S.D. values, after corrections for scan speed, background, Lorentz, and polarization effects. An em-pirical absorption correction, based on the azimuthal scan data, was applied to the data. Crystallographic computations were carried out on a Microvax III com-puter using the NRCC-SDP-VAX structure determina-tion package [14].
A suitable single crystal of 1 was mounted on the top of a glass fiber with glue. Initial lattice parameters were determined from 24 accurately centered reflections with 2u values in the range from 19.42 to 24.34°. Cell constants and other pertinent data were collected and are recorded in Table 1. Reflection data were collected using the u/2u scan method. The final scan speed for each reflection was determined from the net intensity gathered during an initial prescan and ranged from 2.06 to 8.24° min− 1. The u scan angle was determined for
each reflection according to the equation, 0.7090.35 tanu. Three check reflections were measured every 30 min throughout the data collection and showed no apparent decay. The merging of equivalent and dupli-cate reflections gave a total of 2121 unique measured data in which 1703 reflections with I\2s(I) were considered observed. The structure was first solved by using the heavy-atom method (Patterson synthesis), which revealed the positions of metal atoms. The re-maining atoms were found in a series of alternating difference Fourier maps and least-squares refinements. The quantity minimized by the least-squares program was v( Fo − Fc )2, where v is the weight of a given
operation. The analytical forms of the scattering factor tables for the neutral atoms were used [15]. The non-hy-drogen atoms were refined anisotropically. Hynon-hy-drogen atoms were included in the structure factor calculations in their expected positions on the basis of idealized bonding geometry but were not refined in least-squares. The final residuals of this refinement were R = 0.031 and Rw = 0.031. Final values of all refined atomic positional parameters and selected bond distances and angles are listed in Tables 2 and 3, respectively.
The procedures for 3 were similar to those for 1. The unit cell constants were also determined from 24 accu-rately centered reflections. Cell constants and other pertinent data were collected in Table 1. The final residuals of this refinement were R = 0.026 and Rw = 0.028 for 3. Final values of all refined atomic positional parameters and selected bond distances and angles are listed in Tables 4 and 5, respectively. Tables of thermal parameters are given in the supplementary material.
4. Supplementary material
Complete tables of anisotropic thermal parameters, bond distances and bond angles (six pages); listings of observed and calculated structure factors (14 pages) are available from the authors.
Acknowledgements
We thank the National Science Council of Taiwan, Republic of China for support.
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![Fig. 1. ORTEP diagram of the anionic complex [Mo(CO) 4 { h 2 - -S 2 P(OEt) 2 }] − (1).](https://thumb-ap.123doks.com/thumbv2/9libinfo/8670101.195904/2.918.73.868.54.186/fig-ortep-diagram-anionic-complex-mo-s-oet.webp)
