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1.
《Journal of organometallic chemistry》1986,303(2):C47-C51
Reaction of the heterobinuclear complex (CO)4Ru(μ-PPh2)Co(CO)3 with Ph2PCH2PPh2 (dppm) affords the dppm chelate (dppm)(CO)2Ru(μ-PPh2)Co(CO)3 (1) and the dppm bridged molecule (CO)3Ru(μ-PPh2)(μ-dppm)Co(CO)2 (2) both of which have been characterised by X-ray diffraction: 1 is the first binuclear RuCo complex containing a chelating dppm ligand and 2 the first heterobinuclear μ-dppm (RuCo) compound. 相似文献
2.
Leonard Joachim Pereira 《Journal of organometallic chemistry》2005,690(4):1033-1043
TMNO-activated reaction of the heteronuclear cluster Os3Ru(μ-H)2(CO)13 (1) with diphenylphosphine afforded the novel phosphido-bridged clusters Os3Ru(μ-PPh2)(μ-H)3(CO)11 (2), Os3Ru(μ-PPh2)2(μ-H)2(CO)10 (3), Os3Ru(μ-PPh2)2(μ-H)4(CO)9 (4), and Os3Ru(μ-PPh2)(μ-H)3(CO)11(PPh2H) (5). The formation of 2-5 proceeded via P-H bond cleavage in the adduct Os3Ru(μ-H)2(CO)12(PPh2H) (6). Reaction of 2 with PPh3 afforded the adduct Os3Ru(μ-PPh2)(μ-H)3(CO)11(PPh3) (7) and the substituted derivative Os3Ru(μ-PPh2)(μ-H)3(CO)10(PPh3) (8). 相似文献
3.
The novel hydridocobalt(III) complex [mer-Co(H)(SPh)2(PMe3)3] (1) was prepared by reaction of thiophenol with [Co(PMe3)3Cl], [Co(PMe3)4] and [Co(PMe3)4Me]. A dinuclear cobalt dithiophenolato complex [Co(PMe3)2(SPh)]2 (2) was obtained from the reaction of thiophenol with [Co(PMe3)4Me]. Reaction of 1 with iodomethane afforded complex [Co(PMe3)3(I)2] (3). Reaction of complex 2 with carbon monoxide gave a mononuclear dicarbonyl cobalt(I) complex [Co(PMe3)3(CO)2(SPh)] (4). The crystal structures of 1-4 were determined by X-ray diffraction. Formation mechanism of 1 is discussed. 相似文献
4.
Sylviane Sabo Bruno Chaudret Daniele Gervais 《Journal of organometallic chemistry》1983,255(1):C19-C22
Reactions of NaMn(CO)3 with RuCl2(PMe3)4, RuCl2(dppm)2 and RuCl2(PPh3)3 lead either to an ionic species [Ru2Cl3(PMe3)6]+[Mn(CO)5]? or to metal—metal bonded RuMn compounds such as RuMn(μ-CO)2(CO)3(μ-dppm)2 Cl, and, quite unexpectedly, to the μ-phosphido complex RuMn(μ-PPh2)(CO)6(PPh3)2 via a hydride intermediate. 相似文献
5.
《Journal of organometallic chemistry》1987,331(3):341-346
The mixed ligand tetracarbonyl derivatives, cis-M(CO)4(PPh2H)(PPh3) (M Cr, Mo, W) and cis-W(CO)4(PPh2H)(L) (L PEt3, PEt2Ph, PEtPh2) have been prepared from the reaction of M(CO)5PPh2H with L in THF in the presence of potassium t-butoxide. These reactions are accompanied in most instances by the formation of [W(CO)5PPh2]−, [(OC)5M(μ-PPh2)M(CO)5]−, [(OC)5M(μ-PPh2)-M(CO)4(PPh2H)]−, [(OC)4M(μ-PPh2)2M(CO)4]2−, (OC)4M(μ-PPh2)2M(CO)4, and cis-M(CO)4(PPh2H)2. 相似文献
6.
《Journal of organometallic chemistry》1990,385(3):C50-C54
The complex Ru3(CO)6[P(Ph)C(Ph)C(Ph)](μ-PPh2)2 has been obtained by treating (μ-H)Ru3(CO)7(μ-PPh2)3 with C2Ph2 in aliphatic hydrocarbons and its structure has been determined by an X-ray diffraction study. The alkyne inserts into a RuP bond and there is reductive elimination of benzene, formed by coupling of a phenyl group of the μ-PPh2 ligand with the cluster μ-hydride. 相似文献
7.
《Polyhedron》2001,20(15-16):2011-2018
The reaction behavior of the 48e-clusters [Ru3(CO)8(μ-H)2(μ-PR2)2] (R=But, 1a; R=Cy, 1b) towards phosphine ligands has been studied. Whereas 1a reacts spontaneously with many phosphines at room temperature, a lack of reactivity for 1b under similar conditions is observed. Thus 1a reacts with dppm (Ph2PCH2PPh2) to the known 46e-cluster [Ru3(μ-CO)(CO)4(μ3-H)(μ-H)(μ-PBut2)2(μ-dppm)] (2a), and the reaction of 1a with dppe (Ph2PC2H4PPh2) yields analogously [Ru3(μ-CO)(CO)4(μ3-H)(μ-H)(μ-PBut2)2(μ-dppe)] (3). Reactions of 1a with dmpm (Me2PCH2PMe2), dmpe (Me2PC2H4PMe2) and PBun3, respectively, gave in each case a mixture of products which could not be characterized. Contrary to the reaction behavior at room temperature, 1b reacts with phosphines in THF under reflux yielding the novel complexes [Ru3(CO)6(μ-H)2(μ-PCy2)2L2] (L=Cy2PH, 4a; L=But2PH, 4b; L=Ph2PH, 4c; L=P(OEt)3, 4d). 4a is also obtained directly by the reaction of [Ru3(CO)12] with an excess of Cy2PH. The molecular structure of 4a has been determined by a single-crystal X-ray analysis. Moreover, the thermolysis of 1a in octane affords [Ru3(CO)8(μ-H)2(μ3-PBut)(But2PH)] (6) as the main product, and the thermolysis of [Ru3(CO)9(But2PH)(μ-dppm)] (7) yields 2a to a considerable extent. Treatment of 1a with carbon tetrachloride leads to [Ru3(CO)7(μ-H)(μ-PBut2)2(μ-Cl)] (8) as the main product. 相似文献
8.
Michael I Bruce Paul A Humphrey Brian W Skelton 《Journal of organometallic chemistry》2004,689(14):2415-2420
Reactions of Os3(CO)12 with 1,8-bis(diphenylphosphino)naphthalene (dppn) are described. Crystallographically characterised complexes isolated from a reaction carried out in refluxing toluene are Os3(μ-H)2{μ-PPh2(nap)PPh(C6H4)}2(CO)6 (1), Os3(μ-H){μ3-PPh2(nap)PPh(C6H4)}(CO)8 (2) and Os2(μ-PPh2){μ-PPh2(nap)}(CO)5 (3) (nap=1,8-C10H6), while at r.t. in the presence of ONMe3, only Os3(CO)11{PPh2(1-C10H7)} (4) was isolated. While 1 and 2 contain ligands formed by metallation of a Ph group of dppn, as found also in complexes obtained from dppn and Ru3(CO)12, ligands in 3 and 4 are formed by cleavage of a P-nap bond, not found in the Ru series. 相似文献
9.
《Journal of organometallic chemistry》1990,393(2):C30-C33
The reactions of [Ru3(μ-H)(μ-ampy)(CO)9] (1) (Hampy = 2-amino-6-methylpyridine) with one or two equivalents of PPh2H lead to the complexes [Ru3(μ-H)(μ3-ampy)(CO)8(PPh2H)] (2) or [Ru3(μ-H)(μ3-ampy)(CO)7(PPh2H)2] (3), in which the PPh2H ligands are cis to the bridging NH fragment and cis to the hydride. Complex 2 can be transformed in refluxing THF into the phosphido-bridged derivative [Ru3(μ3-ampy)(μ-PPh2)(μ-CO)2(CO)6] (4), which contains the PPh2 ligand spanning one of the two RuRu edges unbridged by the amido moiety, and presents an extremely high 31P chemical shift of 386.9 ppm. Under similar conditions, complex 3 gives a mixture of two isomers of [Ru3(μ-H)(μ3-ampy)(μ-PPh2)2(CO)6] in a 5:1 ratio; the major product (5) has a plane of symmetry, whereas the minor one (6) is asymmetric. 相似文献
10.
Andrew F. Dyke Selby A.R. Knox Pamela J. Naish 《Journal of organometallic chemistry》1980,199(2):C47-C49
Treatment of [Ru2(CO)(μ-CO) {μ-C(O)C2Ph2} (η-C 5H5)2] with allene in toluene at 100°C displaces diphenylacetylene and produces [Ru(CO)(η-C5H5)-{η3-C3H4Ru(CO)2(η-C5H5)}]; upon protonation a 1-methylvinyl cation [Ru2(CO)2(μ-CO){μ-C(Me)CH2}(η-C5H5)2]+ is formed which undergoes nucleophillic attack by hydride to yield the μ-dimethylcarbene complex [Ru2(CO)2-(μ-CO)(μ-CMe2)(η-C5H5)2]. 相似文献
11.
Reaction of Ph2PCC(CH2)5CCPh2 with Os3(CO)10(NCMe)2 affords Os3(CO)10(μ,η2-(Ph2P)2C9H10) (1) and the double cluster [Os3(CO)10]2(μ,η2- (Ph2P)2C9H10)2 (2), through coordination of the phosphine groups. Thermolysis of 1 in toluene generates Os3(CO)7(μ-PPh2)(μ3,η5-Ph2PC9H10) (3) and Os3(CO)8(μ-PPh2)(μ3,η6-Ph2P(C9H10)CO) (4). The molecular structures of 1, 3, and 4 have been determined by an X-ray diffraction study. Both 3 and 4 contain a bridging phosphido group and a carbocycle connected to an osmacyclopentadienyl ring, which are apparently derived from C-P bond activation and C-C bond rearrangement of the dpndy ligand governed by the triosmium clusters. 相似文献
12.
《Journal of organometallic chemistry》1987,323(1):C10-C12
[Ru(CO)4PMe3] reacts with MeI to give fac-[Ru(CO)3(PMe3)(Me)I]. The latter reacts with PMe3 to give a mixture of the three isomers of cis-bis(trimethylphosphine)-cis-dicarbonyl acetyl iodide [Ru(CO)2(PMe3)2(COMe)I]. Decarbonylation of the mixture gives only the trans-bis(trimethylphosphine)-cis-dicarbonyl methyl iodide complex [Ru(CO)2(PMe3)2MeI], which was also prepared by oxidative addition of MeI to [Ru(CO)3(PMe3)2]. 相似文献
13.
Richard P. Rosen Gregory L. Geoffroy Clifford Bueno Melvyn Rowen Churchill Richard B. Ortega 《Journal of organometallic chemistry》1983,254(1):89-103
The new complex Ru3(CO)9(PPh2H)3 (I) was prepared by the direct thermal reaction of Ru3(CO)12 with PPh2 H and was spectroscopically characterized. Irradiation of I with λ ≥ 300 nm leads to the formation of Ru2(μ-PPh2)2(CO)6 (II) and three new phosphido-bridged complexes, Ru3(μ-H)2(μ-PPh2)2(CO)8 (III), Ru3(μ-H)2(μ-PPh2)2(CO)7(PPh2H) (IV) and Ru3(μ-H)(μ-PPh2)3(CO)7 (V). These complexes have been characterized spectroscopically and Ru3 (μ-H)(μ-PPh2)3(CO)7 by a complete single crystal X-ray structure determination. It crystallizes in the space group P21/n with a 20.256(3), b 22.418(6), c 20.433(5) Å, β 112.64(2)°, V 8564(4) Å3, and Z = 8. Diffraction data were collected on a Syntex P21 automated diffractometer using graphite-monochromatized Mo-Kα radiation, and the structure was refined to RF 4.76% and RwF 5.25% for the 8,847 independent reflections with F0 > 6σ(F0). The structure consists of a triangular array of Ru atoms with seven terminal carbonyl ligands, three bridging diphenylphosphido ligands which bridge each of the RuRu bonds, and the hydride ligand which bridges one RuRu bond. Complex IV was also shown to give V upon photolysis and is thus an intermediate in the photoinduced formation of V from I. 相似文献
14.
The complexes of the type [ReH(CO)5–n(PMe3)n] (n = 4, 3) were reacted with aldehydes, CO2, and RC?CCOOMe (R = H, Me) to establish a phosphine-substitutional effect on the reactivity of the Re–H bond. In the series 1–3 , benzaldehyde showed conversion with only 3 to afford a (benzyloxy)carbonyltetrakis(trimethylphosphine)rhenium complex 4 . Pyridine-2-carbaldehyde allowed reaction with all hydrides 1–3 . With 1 and 2 , the same dicarbonyl[(pyridin-2-yl)methoxy-O, N]bis(trimethylphosphine)rhenium 5b was formed with the intermediacy of a [(pyridin-2-yl)methoxy-O]-ligated species and extrusion of CO or PMe3, respectively. The analogous conversion of 3 afforded the carbonyl[(pyridin-2-yl)methoxy-O,N]tris(trimethylphosphine)rhenium ( 1 ) 7b . While 1 did not react with CO2, 2 and 3 yielded under relatively mild conditions the formato-ligated [Re(HCO2)(CO)(L)(PMe3)3] species ( 8 (L = CO) and 9 (L = PMe3)). Methyl propiolate and methyl butynoate were transformed, in the presence of 1 , to [Re{C(CO2Me)?CHR}(CO)3(PMe3)2] systems ( 10a (R = H), and 10b (R = Me)), with prevailing α-metallation and trans-insertion stereochemistry. Similarly, HC≡CCO2Me afforded with 2 and 3 , the α-metallation products [Re{C(CO2Me)?CH2}(CO)(L)(PMe3)3] 11 (L = CO) and 12 (L = PMe3). The methyl butyonate insertion into 2 resulted in formation of a mixture of the (Z)- and (E)-isomers of [Re{C(CO2Me)?CHMe} (CO)2(PMe3)3] ( 13a , b ). In the case of the conversion of 3 with MeC?CCO2Me, a Re–H cis-addition product [Re{(E)-C(CO2Me)?CHMe}(CO)(PMe3)4] ( 14 ) was selectively obtained. Complex 11 was characterized by an X-ray crystal-structure analysis. 相似文献
15.
Arun K. Raha Iqbal Hossain Brian K. Nicholson Luca Salassa 《Journal of organometallic chemistry》2011,696(10):2153-2160
The ruthenium-tin complex, [Ru2(CO)4(SnPh3)2(μ-pyS)2] (1), the main product of the oxidative-addition of pySSnPh3 to Ru3(CO)12 in refluxing benzene, is [Ru(CO)2(pyS)(SnPh3)] synthon. It reacts with PPh3 to give [Ru(CO)2(SnPh3)(PPh3)(κ2-pyS)] (2) and further with Ru3(CO)12 or [Os3(CO)10(NCMe)2] to afford the butterfly clusters [MRu3(CO)12(SnPh3)(μ3-pyS)] (3, M=Ru; 4, M=Os). Direct addition of pySSnPh3 to [Os3(CO)10(NCMe)2] at 70 °C gives [Os3(CO)9(SnPh3)(μ3-pyS)] (5) as the only bimetallic compound, while with unsaturated [Os3(CO)8{μ3-PPh2CH2P(Ph)C6H4}(μ-H)] the previously reported [Os3(CO)8(μ-pyS)(μ-H)(μ-dppm)] (6) and the new bimetallic cluster [Os3(CO)7(SnPh3){μ-Ph2PCH2P(Ph)C6H4}(μ-pyS)[(μ-H)] (7) are formed at 110 °C. Compounds 1, 2, 4, 5 and 7 have been characterized by X-ray diffraction studies. 相似文献
16.
Sylviane Sabo Bruno Chaudret Danièle Gervais 《Journal of organometallic chemistry》1985,292(3):411-418
The possibility of making metal—metal bonded heterobimetallic species by metathesis of ruthenium dichlorides with anionic carbonylates is demonstrated by the isolation of MoRu(μ-Cl)(μ-CO)(CO)2(PPh3)2(η-C5H5) (1) and MnRuCl(μ-CO)2(CO)3(μ-dppm)2 (2), obtained by action of [Mo(CO)3(η-C5H5]? on RuCl2(PPh3)3 and of Mn(CO)5? on RuCl2(dppm)2, respectively. In contrast, reaction of Mn(CO)5? with RuCl2(PMe3)4 yielded an ionic species 3 containing the diruthenium cation Ru2Cl3(PMe3)6+. More interestingly, the action of Mn(CO)5? on RuCl2(PPh3)3 resulted in the formation of the unexpected complex MnRu(μ-PPh2)(CO)6(PPh3)2 (4) in which the phosphido group PPh2 bridges the two metals; this process is shown to involve a hydride intermediate, and elimination of a molecule of benzene, both identified in the reaction mixture. 相似文献
17.
Simon A. Llewellyn Malcolm L.H. Green Andrew R. Cowley 《Journal of organometallic chemistry》2005,690(9):2358-2364
The new cobalt (l) acyl compounds, [Co(PMe3)(CO)3(COMe)] 1, [Co(PPhMe2)(CO)3(COMe)] 2, [Co(P(4-Me-C6H4)3)(CO)3(COMe)] 3 and [Co(P(4-F-C6H4)3)(CO)3(COMe)] 4, have been prepared from [Na(Co(CO)4)]. The compound [Co(PCy3)(CO)3(COMe)] 5 has been prepared from [Co(PCy3)(CO)3(Me)] 6. The crystal structures of 5 and 6 are reported. 相似文献
18.
《Journal of organometallic chemistry》1989,369(2):C27-C32
The dinuclear cobalt complex [CH2(C5H4)2][Co(PMe3)2]2 (2), which is prepared from CoCl(PMe3)3 and [CH2(C5H4)2]Li2, reacts with NH4PF6 and CH3I to form the protonated and methylated dications {[CH2(C5H4)2][CoR(PMe3)2]2}2+ (R = H, CH3). Treatment of {[CH2(C5H4)2][CoCH3(PMe3)2]2}I2 (4) with LiCH3 affords the neutral compound [CH2(C5H4)2][Co(CH3)2(PMe3)]2 (5). Ligand substitution of [CH2(C5H4)2][Co(CO)2]2 (6) with P2Me4 and 1,2-C2H4(PMe2)2(dmpe) gives the doubly-bridged complexes [CH2(C5H4)2][Co2(CO)2(μ-P2Me4)] (7) and [CH2(C5H4)2][Co2(CO)2(μ-dmpe)] (8), respectively. Similarly, [CH2(C5H4)2][Co-(CO)(PMe3)]2 (9) is obtained from the reaction of 6 with PMe3. Oxidation of 6 with iodine gives [CH2(C5H4)2][Co(CO)I2]2 (11) which is transformed via {[CH2(C5H4)2][Co(PMe2H)3]2}I4 (12) into the triply-bridged cobalt(II) complex [CH2(C5H4)2][CO2(μ-PMe2)2] (13). 相似文献
19.
Maria Helena Araujo Maria D. Vargas Anthony G. Avent Fabrizia Grepioni 《Journal of organometallic chemistry》2004,689(22):3513-3519
The reactions of [HIr4(CO)9(Ph2PCCPh)(μ-PPh2)] (1) or [Ir4(CO)8(μ3-η2-HCCPh)(μ-PPh2)2] (2) with HCCPh gave two isomeric forms of [Ir4(CO)6(μ3-η2-HCCPh)(μ2-η4-C4H2Ph2)(μ-PPh2)2] (3 and 4) in good yields as the only products. These compounds were characterized with analytical and spectroscopic data including 1H, 13C and 31P NMR (1 and 2D) spectroscopy and their molecular structures were established by X-ray diffraction studies. Compounds 3 and 4 exhibit the same distorted butterfly metal polyhedral arrangement of metal atoms with two μ-PPh2 that occupy different positions in the structures of the two isomers. Both molecules contain a HCCPh ligand bonded in a μ3-η2-// mode to one of the wings of the butterfly and a metallacyclic ring, which resulted from head-to-tail coupling, in the case of [Ir4(CO)6(μ3-η2-HCCPh){μ2-η4-(H)CC(Ph)C(H)C(Ph)}(μ-PPh2)2] (3) and tail-to-tail coupling, in that of [Ir4(CO)6(μ3-η2-HCCPh){μ2-η4-(H)CC(Ph)C(Ph)C(H)}(μ-PPh2)2] (4), and which is linked to two metal atoms of the second wing of the butterfly. 相似文献
20.
《Journal of organometallic chemistry》2003,665(1-2):15-22
The keto-functionalised N-pyrrolyl phosphine ligand PPh2NC4H3{C(O)CH3-2} L1 reacts with [MoCl(CO)3(η5-C5R5)] (R=H, Me) to give [MoCl(CO)2(L1-κ1P)(η5-C5R5)] (R=H 1a; Me 1b). The phosphine ligands PPh2CH2C(O)Ph (L2) and PPh2CH2C(O)NPh2 (L3) react with [MoCl(CO)3(η5-C5R5)] in an analogous manner to give the compounds [MoCl(CO)2(L-κ1P)(η5-C5R5)] (L=L2, R=H 2a, Me 2b; L=L3, R=H 3a, Me 3b). Compounds 1–3 react with AgBF4 to give [Mo(CO)2(L-κ2P,O)(η5-C5R5)]BF4 (L=L1, R=H 4a, Me 4b; L=L2, R=H 5a, Me 5b; L=L3, R=H 6a, Me 6b) following displacement of chloride. The X-ray crystal structure of 4a revealed a lengthening of both Mo–P and CO bonds on co-ordination of the keto group. The lability of the co-ordinated keto or amido group has been assessed by addition of a range of phosphines to compounds 4–6. Compound 4a reacts with PMe3, PMe2Ph and PMePh2 to give [Mo(CO)2(L1-κ1P)(L)(η5-C5H5)]BF4 (L=PMe3 7a; PMe2Ph 7b; PMePh2 7c) but does not react with PPh3, 5a reacts with PMe2Ph, PMePh2 and PPh3 to give [Mo(CO)2(L2-κ1P)(L)(η5-C5H5)]BF4 (L=PMe2Ph 8b; PMePh2 8c; PPh3 8d), and 6a reacts with PMe3, PMe2Ph, PMePh2 and PPh3 to give [Mo(CO)2(L3-κ1P)(L)(η5-C5H5)]BF4 (L=PMe3 10a; PMe2Ph 10b; PMePh2 10c; PPh3 10d). No reaction was observed for the pentamethylcyclopentadienyl compounds 4b–6b with PMe3, PMe2Ph, PMePh2 or PPh3. These results are consistent with the displacement of the co-ordinated oxygen atom being influenced by the steric properties of the P,O-ligand, with PPh3 displacing the keto group from L2 but not from the bulkier L1. In the reaction of [Mo(CO)2(L2-κ2P,O)(η5-C5H5)]BF4 (5a) with PMe3 the phosphine does not displace the keto group, instead it acts as a base, with the only observed molybdenum-containing product being the enolate compound [Mo(CO)2{PPh2CHC(O)Ph-κ2P,O}(η5-C5H5)] 9. Compound 9 can also be formed from the reaction of 2a with BuLi or NEt3, and a single crystal X-ray analysis has confirmed the enolate structure. 相似文献