ARTICLE pubs.acs.org/Organometallics
Trinuclear and Tetranuclear Ruthenium Carbonyl Clusters Derived from Indenylphosphines: Cleavage of C H and C P Bonds Xing Tan,† Bin Li,† Shansheng Xu,† Haibin Song,† and Baiquan Wang*,†,‡ † ‡
State Key Laboratory of Elemento-Organic Chemistry, College of Chemistry, Nankai University, Tianjin 300071, China State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai 200032, China
bS Supporting Information ABSTRACT: Thermal treatment of Ru3(CO)12 with equimolar amounts of (1H-inden-3-yl)diphenylphosphine and (1Hinden-2-yl)diphenylphosphine in octane gave two isomeric trinuclear ruthenium clusters Ru3(μ2-H)(μ3-3-Ph2PC9H6)(CO)9 (1) and Ru3(μ2-H)(μ3-2-Ph2PC9H6)(CO)9 (2), respectively, via a C H bond cleavage. Heating either 1 or 2 in octane afforded the trinuclear and tetranuclear ruthenium clusters Ru3(μ3-PPh)(μ3-C9H6)(CO)9 (3) and Ru4(μ4-PPh) (μ4-C9H6)(CO)11 (4) via double C P bond cleavage. Thermal treatment of Ru3(CO)12 with (4,7-dimethyl-1H-inden-3yl)diphenylphosphine in octane gave trinuclear ruthenium cluster Ru3(μ2-H)(μ3-3-Ph2PC11H10)(CO)9 (5) via a C H bond cleavage. Heating 5 in octane afforded a trinuclear ruthenium cluster Ru3(μ3-PPh)(μ3-C11H10)(CO)9 (6) and two isomeric tetranuclear ruthenium clusters Ru4(μ3-PPh)(μ2-η5:η1-C11H10)(CO)11 (7) and [Ru4(μ4-PPh)(μ4-C11H10)(CO)11] (8) via double C P bond cleavage. Thermal treatment of Ru3(CO)12 with (3,4,7-trimethyl-1H-inden-1-yl)diphenylphosphine in toluene afforded two trinuclear ruthenium clusters Ru3(μ2-H)2(μ3-3-Ph2PC12H11)(CO)8 (9) via both sp3 and sp2 C H bond cleavage and Ru3(μ2-PPh2)(μ3-η2:η2:η5-C12H13)(CO)6 (10) via a C P bond cleavage. Thermal treatment of Ru3(CO)12 with (3-methyl-1Hinden-1-yl)diphenylphosphine in toluene afforded a trinuclear ruthenium cluster Ru3(μ2-H)(μ3-3-Ph2PC10H8)(CO)9] (11) via a C H bond cleavage. The molecular structures of complexes 1 5 and 7 11 have been determined by single-crystal X-ray diffraction analysis.
’ INTRODUCTION The reactions of Ru3(CO)12 with phosphines have been extensively explored over the past several decades,1 5 and many products derived from C(sp2) H2,4 and C P3,4,5a bond cleavage have been isolated and structurally characterized. However, there are rare examples of C(sp3) H bond activation by ruthenium clusters with assistance from coordinated phosphine atom.5 Indenyl metal complexes have been widely studied due to their diverse and flexible hapticities and the enhanced reactivities both in stoichiometric reactions and in catalysis in comparison to their cyclopentadienyl analogues,6 which is referred to as the indenyl effect.7 Reactions of indene derivatives with Ru3(CO)12 generally afforded the η5-indenyl diruthenium carbonyl complexes,8 but in some cases polynuclear ruthenium clusters with more complicated bonding modes were obtained because of the flexible hapticities of indenyl ligands.9 However, there are very few reports of indyne complexes of metal clusters,10 so it is of interest to establish a convenient way to synthesize them. Presented in this work are reactions of indenylphosphines and their methyl-substituted derivatives with Ru3(CO)12, leading to a series of trinulear and tetranuclear indyne ruthenium carbonyl clusters and several other unexpected products, via C H and C P bond cleavage. Especially, a novel trinuclear ruthenium cluster was formed by methyl C(sp3) H activation, which would be described in detail. r 2011 American Chemical Society
’ RESULTS AND DISCUSSION Reactions of Ru3(CO)12 with (1H-Inden-3-yl)diphenylphosphine and (1H-Inden-2-yl)diphenylphosphine. When Ru3-
(CO)12 reacted with equimolar amounts of (1H-inden-3-yl)diphenylphosphine and (1H-inden-2-yl)diphenylphosphine in refluxing octane for 2 h, two isomeric trinuclear ruthenium clusters Ru3(μ2-H)(μ3-3-Ph2PC9H6)(CO)9 (1) and Ru3(μ2-H)(μ3-2Ph2PC9H6)(CO)9 (2) were obtained in high yields, respectively (Scheme 1). Simply substituted products Ru3(CO)12 nLn were not detected because they may readily lose CO to allow metalation at the indenyl rings, in preference to the phenyl rings. The spectroscopic data of 1 and 2 are consistent with the proposed structure. The IR spectra of 1 and 2 only show terminal carbonyl absorptions at 2086 1960 cm 1. Their 1H NMR spectra show a doublet for the bridging hydride (δ = 18.16 ppm for 1, 17.55 ppm for 2), while their 31P NMR spectra show only a singlet (δ = 35.7 ppm for 1, 35.4 ppm for 2). Single-crystal X-ray diffraction analysis shows that 1 and 2 are isostructural clusters (Figures 1 and 2). Both of them contain a μ3-Ph2PC9H6 unit, which is bonded to one Ru atom through the coordination of the phosphorus atom, Received: January 26, 2011 Published: March 23, 2011 2308
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Scheme 1
Figure 2. ORTEP view of the cluster Ru3(μ2-H)(μ3-2-Ph2PC9H6)(CO)9 (2) showing 30% ellipsoids. Hydrogen atoms except for the μ2-H have been omitted for clarity. Selected bond lengths (Å): Ru(1) Ru(2) 2.742(1), Ru(1) Ru(3) 2.8535(9), Ru(2) Ru(3) 3.016(1), Ru(1) C(10) 2.287(4), Ru(1) C(11) 2.281(4), Ru(2) C(11) 2.094(4), Ru(3) P(1) 2.319(1), Ru(2) H 1.79(5), Ru(3) H 1.69(5), P(1) C(10) 1.776(4), C(10) C(11) 1.435(6).
Chart 1
Figure 1. ORTEP view of the cluster Ru3(μ2-H)(μ3-3-Ph2PC9H6)(CO)9 (1) showing 30% ellipsoids. Hydrogen atoms except for the μ2H have been omitted for clarity. Selected bond lengths (Å): Ru(1) Ru(2) 3.0135(5), Ru(1) Ru(3) 2.7472(5), Ru(2) Ru(3) 2.8453(4), Ru(1) C(30) 2.066(3), Ru(2) P(1) 2.3422(8), Ru(3) C(22) 2.362(3), Ru(3) C(30) 2.241(3), Ru(1) H 1.70(5), Ru(2) H 1.86(5), P(1) C(22) 1.791(3), C(22) C(30) 1.430(4).
to another Ru atom through a σ Ru C bond, and to the third Ru atom in an η2 mode. The structures of 1 and 2 are similar to those of related [Os3(μ2-H)(μ3-RPhPC6H4)(CO)9] (R = Me or Ph) (Chart 1) complexes.11 Heating either 1 or 2 in octane or toluene for 7 h resulted in the formation of two products: trinuclear ruthenium cluster Ru3 (μ3-PPh)(μ3-C9H6)(CO)9 (3) and tetranuclear ruthenium cluster Ru4(μ4-PPh)(μ4-C9H6)(CO)11 (4). By reaction with 1 equiv of
Ru3(CO)12 in refluxing octane for 2 h, 3 could be converted into 4 in moderate yield. The IR spectrum of 4 shows terminal carbonyl absorptions at 2084 1961 cm 1 and two bridging carbonyl absorptions at 1867 and 1828 cm 1, while the IR spectrum of 3 only shows terminal carbonyl absorptions at 2087 1970 cm 1. The 31P NMR spectra of 3 and 4 show only one singlet at δ = 388.7 (for 3) and δ = 262.7 (for 4) ppm, indicating the occurrence of C P bond cleavage. Clusters 3 and 4 gave similar but different 1H NMR signals, which show the presence of only 11 protons with a singlet at δ = 4.10 (for 3) and δ = 2.94 (for 4) ppm assigned to the CH2 group. The structures of clusters 3 and 4 were finally confirmed by single-crystal X-ray diffraction studies (Figures 3 and 4). Cluster 3 consists of an open triangular cluster of Ru atoms, each of which is coordinated by three carbonyl groups. The plane of the three Ru atoms is coordinated on one side by a μ3-PPh ligand and on the opposite side by a μ3-indyne ligand. The Ru Ru bond lengths [Ru(1) Ru(2) = 2.8355(8) Å and Ru(2) Ru(3) = 2.8089(7) Å] are consistent with normal Ru Ru bonding. The μ3-indyne ligand is bound to the Ru3 chain through two σ C Ru bonds and an η2-interaction between C(10), C(11), and Ru(2). This structure is closely related to the known structure of Os3(CO)9(μ2-H)2(μ3-C9H6) (Chart 2), which is formed by reaction of indene with Os3(CO)12.10a In molecule 4, a square Ru4 unit is capped on one side, approximately symmetrically, by a μ4-PPh ligand. The μ4-indyne ligand is capped on the other side as a four-electron donor. The 2309
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Chart 2
Chart 3
Figure 3. ORTEP view of the cluster Ru3(μ3-PPh)(μ3-C9H6) (CO)9 (3) showing 30% ellipsoids. Hydrogen atoms have been omitted for clarity. Selected bond lengths (Å): Ru(1) Ru(2) 2.8355(8), Ru(2) Ru(3) 2.8089(7), Ru(1) C(10) 2.092(4), Ru(1) P(1) 2.294(1), Ru(2) C(10) 2.311(4), Ru(2) C(11) 2.374(4), Ru(2) P(1) 2.429(1), Ru(3) C(11) 2.099(4), Ru(3) P(1) 2.296(1), C(10) C(11) 1.419(5).
Figure 4. ORTEP view of the cluster Ru4(μ4-PPh)(μ4-C9H6)(CO)11 (4) showing 30% ellipsoids. Hydrogen atoms have been omitted for clarity. Selected bond lengths (Å): Ru(1) Ru(2) 2.752(1), Ru(1) Ru(4) 2.885(1), Ru(2) Ru(3) 2.745(1), Ru(3) Ru(4) 2.829(1), Ru(1) P(1) 2.442(1), Ru(1) C(12) 2.403(3), Ru(1) C(13) 2.317(3), Ru(2) P(1) 2.407(1), Ru(2) C(13) 2.145(3), Ru(3) P(1) 2.426(1), Ru(3) C(12) 2.436(3), Ru(3) C(13) 2.328(3), Ru(4) P(1) 2.362(1), Ru(4) C(12) 2.102(3), C(12) C(13) 1.438(4).
ndyne plane is almost perpendicular to the Ru4 plane (the dihedral angle is 91.0°), and the coordinated C C bond is diagonally disposed across the Ru4 square. There are two bridging carbonyl ligands along the shorter Ru Ru edges [Ru(1) Ru(2) and Ru(2) Ru(3)] and nine terminal carbonyl ligands, which is consistent with its IR spectrum. This geometry bears closest resemblance to that of known Ru4(μ4-PR)(μ4-X)(CO)11, where X = alkyne,12 thiophyne,4j and pyrrolyne.4k Lewis and co-workers reported a tetranuclear osmium indyne cluster Os4(μ4-C9H6)(CO)12 (Chart 3), which is the minor product of the reaction of indene
with Os3(CO)12, with a similar “butterfly” arrangement of four metal atoms.10b Synthesis and Characterization of Clusters 5 8. Treatment of Ru3(CO)12 with an equimolar amount of (4,7-dimethyl1H-inden-3-yl)diphenylphosphine in refluxing octane for 30 min afforded a complex Ru3(μ2-H)(μ3-3-Ph2PC9H4Me2)(CO)9 (5) in high yield. The structure of 5 is confirmed by single-crystal X-ray diffraction studies with two independent molecules 5a and 5b cocrystallized in the asymmetric unit (Figure 5). Although the basic shapes of molecules 5a and 5b are the same, the Ru Ru bond lengths of them have a significant difference. In molecule 5b, the bond length of Ru(1) Ru(2) is 2.8245(4) Å, much shorter than the corresponding Ru Ru bond length of 5a [Ru(6) Ru(5) = 3.0055(5) Å]. On the contrary, the bond length of Ru(2) Ru(3) of 5b is 2.9838 (4) Å, much longer than the corresponding Ru Ru bond length of 5a [Ru(5) Ru(4) = 2.8311(5) Å]. The most obvious difference between 5a and 5b is the position of the bridging hydride, which is located and refined crystallographically. Similar to cluster 1, the hydride of 5a is attached to Ru(6) and Ru(5) atoms. However, instead of being attached to the corresponding Ru(1) and Ru(2) atoms, the hydride of 5b is connected to Ru(3) and Ru(2) atoms. Thus, the hydride is connected to the longest Ru Ru edge of each [Ru(6) Ru(5) for 5a, Ru(2) Ru(3) for 5b]. Although two different hydrides appear in the solid state, the 1H NMR spectrum of 5 in CDCl3 solution shows only a broad singlet at δ = 17.58 ppm for the hydride, while the hydride in both 1 and 2 shows a doublet at δ = 18.16 and 17.55 ppm, respectively. These results suggest that molecules 5a and 5b can be transformed each to the other rapidly in solution at room temperature. Its IR spectrum shows only terminal carbonyl absorptions at 2084 1967 cm 1, and its 31P NMR spectrum shows a singlet at δ = 35.2 ppm. Heating 5 in refluxing octane for 2 h afforded a trinuclear ruthenium cluster Ru3(μ3-PPh)(μ3-C11H10)(CO)9 (6) and two isomeric tetranuclear ruthenium clusters Ru4(μ3-PPh)(μ2-η5:η1C11H10)(CO)11 (7) and Ru4(μ4-PPh)(μ4-C11H10)(CO)11 (8) (Scheme 2). However, heating 5 in toluene only afforded cluster 8 in low yield. Because of the close analogy in structures between 2310
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Figure 5. ORTEP view of the cluster Ru3(μ2-H)(μ3-3-Ph2PC9 H4Me2)(CO)9 (5) showing 30% ellipsoids. There are two independent molecules 5a (top) and 5b (bottom) in the unit cell. Hydrogen atoms except for the μ2-H have been omitted for clarity. Selected bond lengths (Å): Ru(1) Ru(2) 2.8245(4), Ru(1) Ru(3) 2.7542(5), Ru(2) Ru(3) 2.9838(5), Ru(1) C(11) 2.070(3), Ru(2) P(1) 2.3487(8), Ru(2) H(1) 1.60(4), Ru(3) C(10) 2.338(3), Ru(3) C(11) 2.291(3), Ru(3) H(1) 1.99(4), P(1) C(10) 1.803(3), C(10) C(11) 1.428(4), Ru(4) Ru(5) 2.8311(5), Ru(4) Ru(6) 2.7513(4), Ru(5) Ru(6) 3.0055(5), Ru(4) C(42) 2.289(3), Ru(4) C(43) 2.244(3), Ru(5) P(2) 2.3498(8), Ru(5) H(2) 1.71(3), Ru(6) C(43) 2.070(3), Ru(6) H(2) 1.72(3), P(2) C(42) 1.790(3), C(42) C(43) 1.444(4).
clusters 3 and 6, and that between the clusters 4 and 8, the features of clusters 6 and 8 will not be described in detail. The structure of cluster 7 was confirmed by single-crystal X-ray diffraction studies (Figure 6). Cluster 7 consists of a tetranuclear metal core exhibiting an open tetrahedral geometry. The top atom Ru(4) is bonded to the Cp ring through a σ C Ru bond [Ru(4) C(13) = 2.093(2) Å]. The other three Ru atoms [Ru(1), Ru(2), Ru(3)] compose a closed triangle, with Ru(1) bonded to the indenyl group through an η5 interaction. The lengths of five Ru C(Cp) bonds are significant different, ranging from 2.188(2) Å [Ru(1) C(14)] to 2.311(2) Å [Ru(1) C(16)]. The dihedral angle between the indenyl plane and the closed Ru3
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triangle plane is 32.7°. There are four Ru Ru bonds, with two normal lengths [Ru(1) Ru(3) = 2.8644(3) Å, Ru(2) Ru(3) = 2.8082(3) Å] and two elongated lengths [Ru(1) Ru(2) = 2.9181(3) Å, Ru(2) Ru(4) = 2.9293(3) Å]. A μ3-PPh ligand is attached to Ru(2), Ru(3), and Ru(4). There are 11 carbonyl ligands, three of which bond to Ru(2), Ru(3), and Ru(4), respectively, two to Ru(1). The C(2) O(2) carbonyl ligand is found to be semibridging the Ru(1) Ru(3) edge [Ru(1) C(2) = 1.882(2) Å, Ru(3) C(2) = 2.951(2) Å, Ru(1) C(2) O(2) = 169.8(2)°], and the rest are considered as terminal carbonyls. The indenyl ligand donates a total of 6 electrons, so this cluster has a total of 64 cluster valence electrons (CVE), which is consistent with 8 skeletal electron pair (SEP) count for an arachno polyhedron from a PSEPT13 viewpoint. The spectroscopic data of 7 are consistent with the proposed structure. Its IR spectrum shows carbonyl absorptions at 2082 1943 cm 1, while its 1 H NMR spectrum shows one doublet at δ = 5.10 ppm and one singlet at δ = 4.76 ppm for the two protons on the Cp ring. Its 31P NMR spectrum shows a singlet at δ = 432.3 ppm, which is consistent with the presence of a μ3-phosphido ligand. In our previous experiment, thermolysis of cluster 1 or 2 in octane afforded the trinuclear indyne cluster 3 as the major product, and only a small amount of tetranuclear indyne cluster 4 was obtained (see Experimental Section). Differently, thermolysis of cluster 5 afforded the tetranuclear indyne cluster 8 as the major product, and the trinuclear indyne cluster 6 and the η5:η1-indenyl tetranuclear cluster 7 as minor products. Additionally, further experiment supports that cluster 4 was formed from cluster 3. Thus, we postulate that cluster 6 could be readily converted to cluster 8. Unfortunately, further conversion of cluster 6 was not carried out due to the poor yield of cluster 6. It is noteworthy that the formation of cluster 7 should involve a [1,3]-H shift on the fivemember ring, but the real mechanism is unknown at present. Synthesis and Characterization of Clusters 9 11. Thermal treatment of Ru3(CO)12 with (3,4,7-trimethyl-1H-inden-1-yl) diphenylphosphine or (3-methyl-1H-inden-1-yl) diphenylphosphine in octane for 4 h afforded only several minor unidentified products. When we changed the solvent to toluene, several products were isolated and characterized. However, the yields of these products are relatively low, with the formation of a large amount of dark solid that was not soluble in common organic solvents. The steric hindrance of the 3-position methyl group of these ligands may discourage the cyclometalation of their simply substituted products [Ru3(CO)12 nLn], which may have poor thermal stability and readily decompose to the unidentified dark solid. Treatment of Ru3(CO)12 with (3,4,7-trimethyl-1H-inden-1yl)diphenylphosphine in refluxing toluene for 4 h gave two major products, Ru3(μ2-H)2(μ3-3-Ph2PC12H11)(CO)8 (9) and Ru3(μ2-PPh2)(μ3-η2:η2:η5-C12H13)(CO)6 (10), in low yield (Scheme 3). The structures of clusters 9 and 10 were confirmed by single-crystal X-ray diffraction studies (Figures 7 and 8). Cluster 9 consists of a closed triangular cluster of Ru atoms capped on side face by an indenyl moiety (C12H11), which is attached to a phosphine atom coordinated to Ru(2). There are three Ru Ru bond interaction, with two normal lengths [Ru(1) Ru(2) = 2.8664(6) Å, Ru(1) Ru(3) = 2.8461(6) Å] and one elongated length [Ru(2) Ru(3) = 2.9828(6) Å]. There are eight terminal carbonyls, three of which are bonded to Ru(1) and Ru(2), respectively, two to Ru(3), and two bridging hydrides (located and refined crystallographically). It is noteworthy that the methylene carbon C(9) is bonded with Ru(3) through an intramolecular sp3 C H bond activation. The lengths of 2311
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Scheme 2
Scheme 3
Figure 6. ORTEP view of the cluster Ru4(μ3-PPh)(μ2-η5:η1C9H4Me2)(CO)11 (7) showing 30% ellipsoids. Hydrogen atoms have been omitted for clarity. Selected bond lengths (Å): Ru(1) Ru(2) 2.9181(3), Ru(1) Ru(3) 2.8644(3), Ru(2) Ru(3) 2.8082(3), Ru(2) Ru(4) 2.9293(3), Ru(1) C(12) 2.246(2), Ru(1) C(13) 2.256(2), Ru(1) C(14) 2.188(2), Ru(1) C(15) 2.257(2), Ru(1) C(16) 2.311(2), Ru(2) P(1) 2.3589(5), Ru(3) P(1) 2.3133(5), Ru(4) P(1) 2.3150(5), Ru(4) C(13) 2.093(2).
C(9) C(10) [1.449(3) Å] and C(10) C(11) [1.410(3) Å] are similar, and the lengths of Ru(3) C(9) [2.172(3) Å], Ru(3) C(10) [2.271(2) Å], and Ru(3) C(11) [2.286(2) Å] are consistent with normal Ru C(sp2) bonding, strongly supporting an η3 coordination mode between C(9), C(10), C(11), and Ru(3). The spectroscopic data for cluster 9 are in good agreement with the X-ray data. Its IR spectrum only shows terminal carbonyl absorptions at 2078 1948 cm 1. In its 1H NMR spectrum, the signals of the hydrides are present as a doublet at δ = 14.41 ppm and a singlet at δ = 16.30 ppm. Its 31P{1H} NMR spectrum shows a singlet at δ = 15.5 ppm, which is significantly shifted to lower frequency in comparison with the clusters 1, 2, and 5 (δ = 35.2 35.7 ppm).
Cluster 10 (Figure 9) consists of a closed triangular cluster of Ru atoms with the μ3-indenyl ligand (C12H13) lying over on one side of the triangular in an η5:η2:η2 mode. On the other side, Ru(1) and Ru(2) are capped by a μ2-PPh2 ligand. There are six terminal carbonyls, two of which are bonded to one Ru atom. The spectroscopic data of 10 are consistent with the proposed structure. The IR spectrum of 10 only shows terminal carbonyl absorptions at 2011 1914 cm 1. In the 1H NMR spectrum, the signals of four protons on the indenyl ring are present as four doublets at δ = 5.29, 4.96, 4.52, and 4.39 ppm. The 31P NMR spectrum shows a singlet at δ = 216.5 ppm, which is consistent with the presence of a μ2-phosphido ligand. A few indenyl ruthenium complexes with η5:η2:η2 coordination mode have been reported, which are obtained by heating indene derivatives with Ru3(CO)12.9a,c,d,f No indyne product was isolated by thermal treatment of Ru3(CO)12 with (3,4,7-trimethyl-1H-inden-1-yl)diphenylphosphine. Thus, we propose the 3-position methyl group of this ligand plays a significant role in the formation of η5:η2:η2-indenyl cluster 10 by suppressing the formation indyne clusters. The examples of methyl C H bond activations promoted by ruthenium clusters are still scarce,5b,9g,14 in most of which the activated methyl group is attached to an aza-heterocycle (e.g., NHC, pyrrole, or pyridine). In these cases, the driving force of the C H activation process is contributed to the chelating ability of the aza-heterocycle ligand, which induces the interaction of a methyl group with the metal atoms. 2312
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Figure 7. ORTEP view of the cluster Ru4(μ4-PPh)2(μ4-C9H4Me2)(CO)11 (8) showing 30% ellipsoids. Hydrogen atoms have been omitted for clarity. Selected bond lengths (Å): Ru(1) Ru(2) 2.7539(4), Ru(1) Ru(4) 2.8312(4), Ru(2) Ru(3) 2.7470(4), Ru(3) Ru(4) 2.8440(4), Ru(1) P(1) 2.4155(7), Ru(1) C(12) 2.434(2), Ru(1) C(13) 2.356(2), Ru(2) P(1) 2.3858(7), Ru(2) C(13) 2.167(2), Ru(3) P(1) 2.4110(7), Ru(3) C(12) 2.522(2), Ru(3) C(13) 2.315(2), Ru(4) P(1) 2.3581(7), Ru(4) C(12) 2.137(2), C(12) C(13) 1.417(3).
Figure 8. ORTEP view of the cluster Ru3(μ2-H)2(μ3-3-Ph2PC12H11)(CO)8] (9) showing 30% ellipsoids. Hydrogen atoms except for the two μ2-H have been omitted for clarity. Selected bond lengths (Å): Ru(1) Ru(2) 2.8664(6), Ru(1) Ru(3) 2.8461(6), Ru(2) Ru(3) 2.9828(6), Ru(1) C(11) 2.101(2), Ru(1) H(1) 1.77(2), Ru(2) P(1) 2.3869(8), Ru(2) H(2) 1.70(2), Ru(3) C(9) 2.172(3), Ru(3) C(10) 2.271(2), Ru(3) C(11) 2.286(2), Ru(3) H(1) 1.77(3), Ru(3) H(2) 1.83(3), P(1) C(12) 1.856(3), C(9) C(10) 1.449(3), C(10) C(11) 1.410(3), C(11) C(12) 1.528(3).
To understand the process of C(sp3) H bond activation in the formation of cluster 9, we further studied the reaction of Ru3(CO)12 with (3-methyl-1H-inden-1-yl)diphenylphosphine. However, no C(sp3) H bond activated product was obtained. Instead, a cyclometalation cluster Ru3(μ2-H)(μ3-3-Ph2PC10H8)
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Figure 9. ORTEP view of the cluster [Ru3(μ2-PPh2)(μ3-η2:η2:η5C12H13)(CO)6] (10) showing 30% ellipsoids. Hydrogen atoms have been omitted for clarity. Selected bond lengths (Å): Ru(1) Ru(2) 2.7483(7), Ru(1) Ru(3) 2.9180(9), Ru(2) Ru(3) 2.9263(7), Ru(1) P(1) 2.315(1), Ru(1) C(20) 2.346(3), Ru(1) C(21) 2.337(3), Ru(2) P(1) 2.311(1), Ru(2) C(22) 2.357(3), Ru(2) C(23) 2.264(3), Ru(3) C(24) 2.241(3), Ru(3) C(25) 2.263(3), Ru(3) C(26) 2.238(3), Ru(3) C(27) 2.214(3), Ru(3) C(28) 2.202(3), C(20) C(21) 1.387(4), C(22) C(23) 1.421(4).
Figure 10. ORTEP view of the cluster [Ru3(μ2-H)(μ3-η1:η2-3Ph2PC9H5Me)(CO)9] (11) showing 30% ellipsoids. Hydrogen atoms except for the μ2-H have been omitted for clarity. Selected bond lengths (Å): Ru(1) Ru(2) 3.015(1), Ru(1) Ru(3) 2.745(1), Ru(2) Ru(3) 2.855(1), Ru(1) C(18) 2.078(7), Ru(1) H 1.70(1), Ru(2) P(1) 2.338(2), Ru(2) H 1.70(1), Ru(3) C(10) 2.360(6), Ru(3) C(18) 2.239(6), P(1) C(10) 1.798(6), C(10) C(18) 1.433(9).
(CO)9 (11, Figure 10) was isolated, which had a structure similar to cluster 1 (Scheme 4). According to these results, the 7-position methyl group of (3,4,7-trimethyl-1H-inden-1-yl)diphenylphosphine ligand seems essential to the C(sp3) H bond activation. We postulate that the steric hindrance of 7-position methyl makes the triruthenium cluster core very close to the 3-position methyl group, thereby enabling oxidative addition of C H bonds to the ruthenium center. 2313
dx.doi.org/10.1021/om200072g |Organometallics 2011, 30, 2308–2317
Organometallics Scheme 4
In summary, we have studied the reactions of a series of indenylphosphines derivatives with Ru3(CO)12, and trinuclear and tetranuclear ruthenium clusters 1 11 were obtained via C H bond and C P bond cleavage. The position of methyl substituents on the indenyl ring strongly affects the mode of C H and C P bond cleavage, but the real mechanism of the formation of these clusters is not very clear. Thermolysis of the cyclometalation clusters 1, 2, and 5 could easily prepare a series of trinuclear and tetranuclear indyne products 3, 4, 6, and 8, via C P bond cleavage. The unexpected η5:η1-indenyl tetranuclear ruthenium cluster 7 and η5:η2:η2-indenyl trinuclear ruthenium cluster 10 were formed via C P bond cleavage as well. The formation of cluster 9 involves intramolecular methyl C(sp3) H bond activation, which represents a rare example of C(sp3) H bond activation by ruthenium clusters with assistance from coordinated phosphine atom. These results may help us gain more insights into the reactivities of indenylphosphine derivatives toward ruthenium complexes and promote their application in catalysis.
’ EXPERIMENTAL SECTION General Considerations. Schlenk- and vacuum-line techniques were employed for all manipulations. All solvents were distilled from appropriate drying agents under argon before use. 1H and 31P NMR spectra were recorded on a Bruker AV400 spectrometer. IR spectra were recorded as KBr disks on a Nicolet 380 FT-IR spectrometer. Elemental analyses were performed on a Perkin-Elmer 240C analyzer by Prof. Jianxin Ma of the state key laboratory. (1H-Inden-3-yl)diphenylphosphine,15 (1H-inden-2-yl)diphenylphosphine,16 (4,7-dimethyl-1H-inden-3-yl)diphenylphosphine,17 (3,4,7-trimethyl-1H-inden-1-yl)diphenylphosphine,17 and (3-methyl-1H-inden-1-yl)diphenylphosphine17 were prepared according to the literature procedures. Reaction of Ru3(CO)12 with (1H-Inden-3-yl)diphenylphosphine. A solution of Ru3(CO)12 (150 mg, 0.235 mmol) and (1Hinden-3-yl)diphenylphosphine (71 mg, 0.236 mmol) in octane (30 mL) was refluxed for 2 h to give a dark orange solution. After removal of solvent in vacuo, the residue was chromatographed on silica with petroleum ether/CH2Cl2 (8/1) as eluent. The first band gave a trace of unreacted Ru3(CO)12. The second band afforded complex 1 (169 mg, 84%) as an orange solid. Mp 168 169 °C (dec). Anal. Calcd for C30H17 O9PRu3: C, 42.11; H, 2.00. Found: C, 42.37; H, 2.21. 1H NMR (CDCl3): δ 7.90 (s, 2H, Ar H), 7.55 (s, 3H, Ar H), 7.40 7.27 (m, 5H, Ar H), 7.23 (d, J = 7.2 Hz, 1H, Ar H), 7.10 6.95 (m, 3H, Ar H), 4.24 (d, J = 22.1 Hz, 1H, CH2), 3.92 (d, J = 22.4 Hz, 1H, CH2), 18.16 (d, J = 17.3 Hz, 1H, μ2-H) ppm. 31P{1H} NMR (CDCl3): δ 35.7 (s) ppm. IR (νCO, cm 1): 2085 (s), 2057 (s), 2022 (s), 2002 (s), 1987 (s), 1970 (s), 1960 (s).
Reaction of Ru3(CO)12 with (1H-Inden-2-yl)diphenylphosphine. Using a procedure similar to that described for the synthesis of 1, reaction of Ru3(CO)12 (150 mg, 0.235 mmol) and (1H-inden-2-yl) diphenylphosphine (71 mg, 0.236 mmol) in refluxing octane (30 mL)
ARTICLE
for 2 h gave complex 2 (145 mg, 72%) as an orange solid. Mp 160 161 °C (dec). Anal. Calcd for C30H17O9PRu3: C, 42.11; H, 2.00. Found: C, 42.43; H, 2.14. 1H NMR (CDCl3): δ 7.91 (br s, 2H, Ar H), 7.86 (s, 1H, Ar H), 7.56 (s, 3H, Ar H), 7.28 (br s, 8H, Ar H), 3.75 (m, 2H, CH2), 17.55 (d, J = 18.6 Hz, 1H, μ2-H) ppm. 31P{1H} NMR (CDCl3): δ 35.4 (s) ppm. IR (νCO, cm 1): 2086 (s), 2054 (s), 2029 (s), 1998 (s), 1968 (s). Thermolysis of Complex 1. A solution of 1 (165 mg, 0.193 mmol) in octane (30 mL) was refluxed for 7 h to give a dark brown solution. After removal of solvent in vacuo, the residue was chromatographed on silica with petroleum ether/CH2Cl2 (15/1) as eluent. The first band gave complex 3 (58 mg, 39%) as a yellow solid. From the second band, unreacted 1 (69 mg, 42%) was recovered. The third band afforded complex 4 (6 mg, 4%) as a red solid. Complex 3. Mp 155 156 °C (dec). Anal. Calcd for C24H11O9PRu3: C, 37.07; H, 1.43. Found: C, 37.18; H, 1.63. 1H NMR (CDCl3): δ 8.00 (d, J = 6.1 Hz, 1H, Ar H), 7.58 (m, 2H, Ar H), 7.41 (s, 3H, Ar H), 7.30 (m, 3H, Ar H), 4.10 (s, 2H, CH2) ppm. 31P{1H} NMR (CDCl3): δ 388.7 (s) ppm. IR (νCO, cm 1): 2087 (m), 2062 (s), 2049 (s), 2003 (s), 1970 (s). Complex 4. Mp 175 176 °C (dec). Anal. Calcd for C26H11O11PRu4: C, 33.41; H, 1.19. Found: C, 33.25; H, 1.31. 1H NMR (CDCl3): δ 8.10 (d, J = 7.4 Hz, 1H, Ar H), 7.25 7.17 (m, 5H, Ar H), 6.90 (d, J = 7.1 Hz, 1H, Ar H), 6.59 (dd, J = 7.2, 14.5 Hz, 2H, Ar H), 2.94 (s, 2H, CH2) ppm. 31P{1H} NMR (CDCl3): δ 262.7 (s) ppm. IR (νCO, cm 1): 2084 (s), 2030 (s), 1993 (s), 1961 (s), 1867 (m), 1828 (s). Thermolysis of Complex 2. Using a procedure similar to that described for the thermolysis of 1, thermolysis of 2 in refluxing octane gave complex 3 (45 mg, 43%), unreacted 2 (30 mg, 26%), and complex 4 (4 mg, 4%). Reaction of Ru3(CO)12 with Complex 3. A solution of Ru3(CO)12 (87 mg, 0.136 mmol) and 3 (106 mg, 0.136 mmol) in octane (20 mL) was refluxed for 2 h to give a dark brown solution (TLC revealed no presence of 3). After removal of solvent in vacuo, the residue was chromatographed on silica with petroleum ether/CH2Cl2 (15/1) as eluent to give two bands. From the first band, 29 mg (33%) of unreacted Ru3(CO)12 was recovered. The second band afforded 52 mg (41%) of 4.
Reaction of Ru3(CO)12 with (4,7-Dimethyl-1H-inden-3yl)diphenylphosphine. Using a procedure similar to that described for the synthesis of 1, reaction of Ru3(CO)12 (150 mg, 0.235 mmol) and (4,7-dimethyl-1H-inden-3-yl)diphenylphosphine (78 mg, 0.236 mmol) in refluxing octane (30 mL) for 30 min gave 183 mg (88%) of complex 5 as an orange solid. Mp 159 160 °C (dec). Anal. Calcd for C32H21O9PRu3: C, 43.49; H, 2.40. Found: C, 43.54; H, 2.37. 1H NMR (CDCl3): δ 7.48 7.21 (m, 8H, Ar H), 7.02 (br s, 2H, Ar H), 6.84 (d, J = 7.7 Hz, 1H, Ar H), 6.73 (d, J = 7.6 Hz, 1H, Ar H), 4.30 (s, 2H, CH2), 2.31 (s, 3H, CH3), 1.33 (s, 3H, CH3), 17.58 (s, 1H, μ2-H) ppm. 31P{1H} NMR (CDCl3): δ 35.2 (s) ppm. IR (νCO, cm 1): 2084 (s), 2054 (s), 2028 (s), 1992 (s), 1967 (s). Thermolysis of Complex 5. A solution of 5 (127 mg, 0.144 mmol) in octane (30 mL) was refluxed for 2 h to give a dark brown solution. After removal of solvent in vacuo, the residue was chromatographed on silica with petroleum ether as eluent. The first band gave a mixture of complexes 6 and 7 as a red oil. Further purification of the mixture by recrystallization with hexane gave 10 mg (9%) of 6 as a yellow solid and 4 mg (4%) of 7 as a red solid. From the second band, 46 mg (36%) of unreacted 5 was recovered. The third band afforded 23 mg (22%) of complex 8 as a red-brown solid. Complex 6. Mp 169 170 °C (dec). Anal. Calcd for C26H15O9PRu3: C, 38.76; H, 1.88. Found: C, 38.99; H, 2.03. 1H NMR (CDCl3): δ 7.68 (d, J = 6.9 Hz, 2H, Ar H), 7.41 7.34 (m, 3H, Ar H), 7.02 (d, J = 7.1 Hz, 1H, Ar H), 6.93 (d, J = 7.2 Hz, 1H, Ar H), 3.69 (s, 2H, CH2), 2.46 (s, 3H, CH3), 2.38 (s, 3H, CH3) ppm. 31P{1H} NMR (CDCl3): δ 391.8 (s) ppm. IR (νCO, cm 1): 2082 (s), 2053 (s), 2027 (s), 2013 (s), 1985 (s). 2314
dx.doi.org/10.1021/om200072g |Organometallics 2011, 30, 2308–2317
Organometallics
ARTICLE
Table 1. Crystal Data and Summary of X-ray Data Collection 1
2
3
4
5
formula
C30H17O9PRu3
C30H17O9PRu3
C24H11O9PRu3
C26H11O11PRu4
C32H21O9PRu3
fw
855.62
855.62
777.51
934.60
883.67
T, K
116(2)
113(2)
113(2)
113(2)
113(2)
λ, Å
0.71073
0.71073
0.71073
0.71073
0.71075
cryst syst
monoclinic
monoclinic
monoclinic
triclinic
triclinic
space group
C2/c
P21/c
P21/c
P-1
P-1
a, Å
17.169(3)
18.744(8)
12.050(2)
9.612(5)
10.6366(17)
b, Å c, Å
17.272(3) 20.228(3)
9.235(4) 20.328(8)
10.849(2) 19.484(4)
11.728(6) 15.382(7)
12.3945(18) 24.119(4) 95.952(3)
R, deg
90
90
90
102.577(6)
β, deg
98.088(2)
113.306(6)
99.56(3)
97.249(7)
98.672(2)
γ, deg
90
90
90
108.782(5)
90.097(4)
V, Å3
5938.5(17)
3232(2)
2511.8(9)
1565.7(14)
3126.0(9)
Z
8
4
4
2
4
1.914
1.759
2.056
1.982
1.878
1.614 3328
1.483 1664
1.896 1496
1.997 892
1.536 1728
Dcalc, g cm μ, mm F(000)
3
1
cryst size, mm
0.30 0.26 0.20
0.20 0.18 0.12
0.20 0.18 0.12
0.22 0.18 0.16
0.26 0.22 0.20
θ range, deg
1.68 25.02
2.03 25.02
1.71 25.02
1.91 27.92
1.65 27.88
no. of reflns collected
20 418
21 429
13 736
19 236
29 654
no. of indep reflns/Rint
5251/0.0684
5691/0.0282
4412/0.0406
7465/0.0379
14 566/0.0358
no. of params
393
392
372
379
824
GOF on F2
0.770
1.095
1.005
1.027
0.965
R1, wR2 [I > 2σ(I)] R1, wR2 (all data)
0.0442, 0.1154 0.0448, 0.1175
0.0207, 0.0539 0.0225, 0.0545
0.0331, 0.0749 0.0364, 0.0766
0.0250, 0.0629 0.0310, 0.0641
0.0267, 0.0561 0.0347, 0.0586
largest diff. peak and hole (e Å 3)
1.077,
0.429,
1.021,
0.775,
0.737,
1.664 7
0.575 8
1.167 9
0.856 10
0.700 11
formula
C28H15O11PRu4
C28H15O11PRu4
C32H23O8PRu3
C30H23O6PRu3
C31H19O9PRu3
fw
962.65
962.65
869.68
813.66
869.64
T, K
113(2)
113(2)
113(2)
113(2)
116(2)
λ, Å
0.71075
0.71075
0.71073
0.71073
0.71073
cryst syst space group
monoclinic P21/c
triclinic P-1
monoclinic P21/c
triclinic P-1
monoclinic C2/c
a, Å
10.2070(10)
8.8717(8)
11.529(2)
9.6491(19)
17.663(7)
b, Å
15.6790(14)
10.0624(9)
18.246(4)
9.951(2)
16.873(6)
c, Å
19.527(2)
16.6570(15)
14.917(3)
15.950(3)
20.306(7)
R, deg
90
77.613(5)
90
86.84(3)
90
β, deg
104.427(5)
85.545(7)
101.79(3)
79.00(3)
95.605(5)
γ, deg
90
88.201(6)
90
66.39(3)
90
V, Å3 Z
3026.5(5) 4
1447.8(2) 2
3071.6(11) 4
1377.1(5) 2
6023(4) 8
2.113
2.208
1.881
1.962
1.918
2.070
2.163
1.559
1.726
1.593
F(000)
1848
924
1704
796
3392
cryst size, mm
0.22 0.18 0.16
0.06 0.04 0.04
0.20 0.06 0.04
0.18 0.16 0.12
0.20 0.14 0.10
Dcalc, g cm μ, mm
3
1
θ range, deg
1.69 37.83
1.25 27.95
2.12 25.02
2.34 25.02
1.89 25.02
no. of reflns collected
60 815
18 328
23 170
11 254
17 610
no. of indep reflns/Rint no. of params
15 633/0.0414 399
6905/0.0300 399
5419/0.0376 408
4824/0.0245 364
5153/0.0338 402
GOF on F2
1.132
1.007
1.095
1.069
1.138
R1, wR2 [I > 2σ(I)]
0.0326, 0.0695
0.0241/0.0441
0.0237, 0.0579
0.0231, 0.0580
0.0422/0.1436
R1, wR2 (all data)
0.0385, 0.0726
0.0316/0.0459
0.0264, 0.0590
0.0259, 0.0592
0.0430/0.1440
largest diff. peak and hole (e Å 3)
0.816,
0.693,
0.594,
0.997,
1.718,
1.790
0.619 2315
0.530
0.642
0.960
dx.doi.org/10.1021/om200072g |Organometallics 2011, 30, 2308–2317
Organometallics Complex 7. Mp 158 159 °C (dec). Anal. Calcd for C28H15O11PRu4: C, 34.93; H, 1.57. Found: C, 34.97; H, 1.63. 1H NMR (CDCl3): δ 7.59 (t, J = 8.8 Hz, 2H, Ar H), 7.42 7.32 (m, 3H, Ar H), 6.90 (d, J = 6.9 Hz, 1H, Ar H), 6.79 (d, J = 7.0 Hz, 1H, Ar H), 5.10 (d, J = 1.4 Hz, 1H, CH2), 4.76 (s, 1H, CH2), 2.33 (s, 3H, CH3), 2.17 (s, 3H, CH3) ppm. 31 1 P{ H} NMR (CDCl3): δ 432.3 (s) ppm. IR (νCO, cm 1): 2082 (s), 2061 (s), 2016 (s), 1992 (s), 1982 (s), 1967 (s), 1943 (s). Complex 8. Mp 149 150 °C (dec). Anal. Calcd for C28H15O11PRu4: C, 34.93; H, 1.57. Found: C, 35.14; H, 1.70. 1H NMR (CDCl3): δ 7.24 7.19 (m, 3H, Ar H), 6.98 (d, J = 7.5 Hz, 1H, Ar H), 6.89 (d, J = 7.5 Hz, 1H, Ar H), 6.68 (dd, J = 7.0, 14.4 Hz, 2H, Ar H), 3.17 (s, 3H, CH3), 2.83 (s, 2H, CH2), 1.95 (s, 3H, CH3) ppm. 31P{1H} NMR (CDCl3): δ 269.1 (s) ppm. IR (νCO, cm 1): 2078 (m), 2024 (s), 2002 (s), 1971 (s), 1842 (m).
ARTICLE
in clusters 2 and 4 have been treated by the Platon Squeeze18 routine. All calculations were carried out using the SHELXL-97 program system. All non-hydrogen atoms were refined anisotropically. Hydrogen atoms were assigned idealized positions and were included in structure factor calculations. The crystal data and summary of X-ray data collection for complexes 1 5, 7 11 are presented in Table 1. In 3, the phenyl group attached to the P atom is rotational disordered.
’ ASSOCIATED CONTENT
bS
Supporting Information. Crystallographic details for 1 5 and 7 11 in CIF format. This material is available free of charge via the Internet at http://pubs.acs.org.
Reaction of Ru3(CO)12 with (3,4,7-Trimethyl-1H-inden-1yl)diphenylphosphine. A solution of Ru3(CO)12 (120 mg, 0.188
’ AUTHOR INFORMATION
mmol) and (3,4,7-trimethyl-1H-inden-1-yl)diphenylphosphine (193 mg, 0.564 mmol) in toluene (20 mL) was refluxed for 4 h to give a dark solution. After removal of solvent in vacuo, the residue was chromatographed on silica with petroleum ether/CH2Cl2 (8/1) as eluent. The first band gave 17 mg (10%) of complex 9 as a yellow solid. The second band afforded 23 mg (15%) of complex 10 as a red solid. Complex 9. Mp 172 173 °C (dec). Anal. Calcd for C32H23O8PRu3: C, 44.19; H, 2.67. Found: C, 43.79; H, 2.31. 1H NMR (CDCl3): δ 7.97 (t, J = 8.0, 9.6 Hz, 2H, Ar H), 7.67 7.60 (m, 3H, Ar H), 7.20 7.10 (m, 2H, Ar H), 7.02 6.96 (m, 2H, Ar H), 6.77 (d, J = 7.5 Hz, 1H, Ar H), 6.47 (d, J = 7.5 Hz, 1H, Ar H), 6.07 (d, J = 14.0 Hz, 1H, Ar H), 3.79 (d, J = 3.6 Hz, 1H, CH), 2.60 (d, J = 9.5 Hz, 1H, CH2), 2.52 (d, J = 9.5 Hz, 1H, CH2), 2.51 (s, 3H, CH3), 1.71 (s, 3H, CH3), 14.41 (d, J = 16.0 Hz, 1H, μ2-H), 16.30 (s, 1H, μ2-H) ppm. 31P{1H} NMR (CDCl3): δ 15.5 (s) ppm. IR (νCO, cm 1): 2078 (s), 2048 (s), 2017 (s), 2000 (s), 1988 (s), 1977 (s), 1959 (s), 1948 (s). Complex 10. Mp 195 196 °C (dec). Anal. Calcd for C30H23O6PRu3: C, 44.28; H, 2.85. Found: C, 43.90; H, 2.59. 1H NMR (CDCl3): δ 8.23 8.17 (m, 2H, Ar H), 7.51 (t, J = 6.9, 7.1 Hz, 2H, Ar H), 7.45 (d, J = 7.0 Hz, 1H, Ar H), 7.24 7.16 (m, 3H, Ar H), 6.93 6.88 (m, 2H, Ar H), 5.29 (d, J = 1.4 Hz, 1H, Ar H), 4.96 (d, J = 6.5 Hz, 1H, C5-ring H), 4.52 (d, J = 6.3 Hz, 1H, C5-ring H), 4.39 (d, J = 1.6 Hz, 1H, Ar H), 2.74 (s, 3H, CH3), 2.48 (s, 3H, CH3), 1.78 (s, 3H, CH3) ppm. 31P{1H} NMR (CDCl3): δ 216.5 (s) ppm. IR (νCO, cm 1): 2011 (s), 1976 (s), 1924 (s), 1914 (s).
Corresponding Author
Reaction of Ru3(CO)12 with (3-Methyl-1H-inden-1-yl)diphenylphosphine. A solution of Ru3(CO)12 (120 mg, 0.188 mmol) and (3-methyl-1H-inden-1-yl)diphenylphosphine (60 mg, 0.190 mmol) in toluene (20 mL) was refluxed for 4 h to give a dark brown solution. After removal of solvent in vacuo, the residue was chromatographed on silica with petroleum ether/CH2Cl2 (5/1) as eluent. The major band gave 15 mg (9%) of complex 11 as an orange solid. Mp 170 171 °C (dec). Anal. Calcd for C31H19O9PRu3: C, 42.81; H, 2.20. Found: C, 42.93; H, 2.43. 1 H NMR (CDCl3): δ 7.88 (s, 2H, Ar H), 7.54 (s, 3H, Ar H), 7.42 7.28 (m, 6H, Ar H), 7.22 (d, J = 6.2 Hz, 1H, Ar H), 7.07 6.99 (m, 2H, Ar H), 3.98 (q, J = 7.2 Hz, 1H, CH), 0.99 (d, J = 7.0 Hz, 3H, CH3), 18.25 (d, J = 18.3 Hz, 1H, μ2-H) ppm. 31P{1H} NMR (CDCl3): δ 36.4 (s) ppm. IR (νCO, cm 1): 2085 (s), 2057 (s), 2021 (s), 2001 (s), 1987 (s), 1971 (s), 1957 (s). Crystallographic Studies. Single crystals suitable for X-ray diffraction analysis were grown from hexane/CH2Cl2 (for 1, 2, 5, and 8 11) and hexane (for 7) solution at room temperature, or from hexane (for 3) and toluene/CH2Cl2 (for 4) solution at 20 °C. Data collection was performed on a Rigaku Saturn 70 diffractometer equipped with a rotating anode system by using graphite-monochromated Mo KR radiation (ω 2θ scans). Semiempirical absorption corrections were applied for all complexes. The structures were solved by direct methods and refined by full-matrix least-squares. The disordered solvent molecules
*Fax: 86-22-23504781. E-mail:
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