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1.
Michael I. Bruce Natasha N. Zaitseva Allan H. White 《Journal of organometallic chemistry》2005,690(13):3268-3277
Complexes containing C4 ligands attached to one or two AuRu3 clusters by conventional σ, 2π interactions have been obtained from reactions between (R3P)AuC≡CC≡CAu(PR3) (R = Ph, tol) or Au(C≡CC≡CH){P(tol)3} and either Ru3(CO)12, Ru3(CO)10(NCMe)2 or Ru3(μ-dppm)(CO)10. The X-ray determined structures of {(R3P)AuRu3(CO)9}2(μ3,η2:μ3,η2-C2C2) [R = Ph (1) (three solvates), tol (2)], AuRu3{μ3,η2-C2C≡CAu(PPh3)}(CO)9(PPh3) (3) and {(Ph3P)AuRu3(μ-dppm)(CO)7} (μ3,η2:μ3,η2-C2C2){Ru3(μ-H)(μ-dppm)(CO)7} (4) are reported. 相似文献
2.
《Journal of organometallic chemistry》1987,319(2):239-246
Reaction of C2(PPh2)2(dppa) with Os3(CO)11(NCMe) affords the yellow complex [Os3(CO)11]2(μ-dppa); this on heating gives [Os5(μ5-η2-P-C2PPh2)(μ-PPh2)(CO)13] in 51% yield, which is shown by an X-ray study to contain a seven electron donor C2PPh2 ligand interacting with all five Os5 atoms of an open Os5 cluster consisting of three edge fused Os3 triangles with a “swallowlike” arrangement. The PPh2 group bridges the non fused edgeof the central triangle. The structure appears to be identical with that described for the equivalent ruthenium complex. 相似文献
3.
Syed J. Ahmed Shariff E. Kabir Antony J. Deeming Ebbe Nordlander 《Journal of organometallic chemistry》2006,691(3):309-322
Treatment of [Ru3(CO)10(μ-dppm)] (4) [dppm = bis(diphenylphosphido)methane] with tetramethylthiourea at 66 °C gave the previously reported dihydrido triruthenium cluster [Ru3(μ-H)2(μ3-S)(CO)7(μ-dppm)] (5) and the new compounds [Ru3(μ3-S)2(CO)7(μ-dppm)] (6), [Ru3(μ3-S)(CO)7(μ3-CO)(μ-dppm)] (7) and [Ru3(μ3-S){η1-C(NMe2)2}(CO)6(μ3-CO)(μ-dppm)] (8) in 6%, 10%, 32% and 9% yields, respectively. Treatment of 4 with thiourea at the same temperature gave 5 and 7 in 30% and 10% yields, respectively. Compound 7 reacts further with tetramethylthiourea at 66 °C to yield 6 (30%) and a new compound [Ru3(μ3-S)2{η1-C(NMe2)2}(CO)6(μ-dppm)] (9) (8%). Thermolysis of 8 in refluxing THF yields 7 in 55% yield. The reaction of 4 with selenium at 66 °C yields the new compounds [Ru3(μ3-Se)(CO)7(μ3-CO)(μ-dppm)] (10) and [Ru3(μ3-Se)(μ3-η3-PhPCH2PPh(C6H4)}(CO)6(μ-CO)] (11) and the known compounds [Ru3(μ-H)2(μ3-Se)(CO)7(μ-dppm)] (12) and [Ru4(μ3-Se)4(CO)10(μ-dppm)] (13) in 29%, 5%, 2% and 5% yields, respectively. Treatment of 10 with tetramethylthiourea at 66 °C gives the mixed sulfur-selenium compounds [Ru3(μ3-S)(μ3-Se)(CO)7(μ-dppm)] (14) and [Ru3(μ3-S)(μ3-Se){η1-C(NMe2)2}(CO)6(μ-dppm)] (15) in 38% and 10% yields, respectively. The single-crystal XRD structures of 6, 7, 8, 10, 14 and 15 are reported. 相似文献
4.
Reaction of the square antiprismatic cluster [ppn][Ru8(μ8-P)(μ-CO)2(CO)20] [ppn = bis(triphenylphosphoranylidene)ammonium] with triphenylphosphine proceeds by loss of one cluster core vertex, phosphine P-C cleavage, and CO insertion into the putative Ru-phenyl bond to afford [ppn][Ru7(μ7-P)(μ-η2-OCPh)(μ-PPh2)(μ-CO)(CO)17] in low yield, the first heptaruthenium μ7-phosphido-ligated cluster. 相似文献
5.
Md. Iqbal Hyder Md. Delwar H. Sikder Graeme Hogarth Shariff E. Kabir Christian J. Richard 《Journal of organometallic chemistry》2009,694(2):304-174
Reaction of [Ru3(CO)10(μ-dppm)] (1) with H2S at 66 °C affords high yields of the sulfur-capped dihydride [Ru3(CO)7(μ-H)2(μ-dppm)(μ3-S)] (2), formed by oxidative-addition of both hydrogen-sulfur bonds. Hydrogenation of [Ru3(CO)7(μ-dppm)(μ3-CO)(μ3-S)] (3) at 110 °C also gives 2 in similar yields, while hydrogenation of [Ru3(CO)7(μ-dppm)(μ3-CO)(μ3-Se)] (4) affords [Ru3(CO)7(μ-H)2(μ-dppm)(μ3-Se)] (5) in 85% yield. The molecular structures of 2 and 5 reveal that the diphosphine and one hydride simultaneously bridge the same ruthenium-ruthenium edge with the second hydride spanning one of the non-bridged edges. Both 2 and 5 are fluxional at room temperature being attributed to hydride migration between the non-bridged edges. Addition of HBF4 to 2 affords the cationic trihydride [Ru3(CO)7(μ-H)3(μ-dppm)(μ3-S)][BF4] (6) in which the hydrides are non-fluxional due to the blocking of the free ruthenium-ruthenium edge. 相似文献
6.
The sodium benzophenone ketyl-induced reaction of [Ru3(CO)12] with bis(diphenylphosphanyl)amine Ph2PN(H)PPh2 (dppa) in THF resulted in the formation of the expected metal cluster [Ru3(CO)10(μ-dppa)] ( 1 ) in high yield. 1 was fully characterized by spectroscopic means and crystals of the compound suitable for X-ray diffraction were obtained from dichloromethane/dioxane. The molecular structure of 1 as its dioxane solvate was determined by X-ray crystallography. The compound crystallized in a new crystal structure of [Ru3(CO)10(μ-dppa)] in the triclinic space group P1 , whereas that compound was described in an earlier report crystallizing from chloroform in the monoclinic space group P21/c. 相似文献
7.
Reaction of W(η2-PhCCPh)3(NMe3) (1) and Ph2PCCPPh2 (dppa) produces W(η2-PhCCPh)3(η1-Ph2PCCPPh2) (2), which contains a pendant phosphine group. Treatment of 2 with W(CO)4(NCMe)2 yields [W(η2-PhCCPh)3](μ,η2-Ph2PCCPPh2)[W(CO)4(NCMe)] (3). Compound 2 reacts with Os3(CO)10(NCMe)2 to afford Os3(CO)10[(μ,η2-Ph2PCCPPh2)W(η2-PhCCPh)3]2 (4), and reacts with Ru3(CO)9(NCMe)3 to afford Ru3(CO)9[(μ,η2-Ph2PCCPPh2)W(η2-PhCCPh)3]3 (5). The crystal structures of 2 and 3 are determined by an X-ray diffraction study. 相似文献
8.
《Journal of organometallic chemistry》2004,689(3):552-556
The compounds [Ru3(CO)9(μ,η2-SCCR)(μ3,η2-CCR′)] (R=SiMe3, R′=SiiPr3 (1); R=SiiPr3, R′=SiMe3 (2); R=SiiPr3, R′=H (3); R=H, R′=SiiPr3 (4)) have been obtained by cleavage of one S-C bond of the thioethers iPr3SiCCSCCR (R=H, SiMe3) in the presence of Ru3(CO)12. Thermal treatment of [Ru3(CO)9(μ,η2-SCCSiiPr3)(μ3,η2-CCH)] yields to the cluster [Ru4(CO)9(μ-CO)2(μ4-S)(μ4-η2-C(H)C)(CCSiiPr3)] (5) which contains a bridging sulfur atom and a polycarbon chain as a consequence of the rupture of the S-C bond and a C-C coupling reaction. All derivatives have been characterized by spectroscopic data. An X-ray diffraction study was carried out on the species [Ru3(CO)9(μ,η2-SCCSiiPr3)(μ3,η2-CCSiMe3)] and of [Ru3(CO)9(μ,η2-SCCSiiPr3)(μ3,η2-CCH)]. 相似文献
9.
Michael I. Bruce Maryka Gaudio Giovanni Melino Natasha N. Zaitseva Brian K. Nicholson Brian W. Skelton Allan H. White 《Journal of Cluster Science》2008,19(1):147-170
Several new gold-containing cluster complexes have been prepared from the reactions of gold alkynyl complexes, L
n
M-C
x
-Au(PPh3), (x = 3, 4, 6) with Ru3(CO)10(NCMe)2. The bis-cluster complex 1,4-{AuRu3(CO)9(PPh3)(μ3-C2)}2C6H4 was obtained from Ru3(CO)10(NCMe)2 and 1,4-{(Ph3P)Au(C≡C)}2C6H4. The complexes Ru3(μ-H){μ3-C2C≡C[Ru(PP)Cp′]}(CO)9 [PP = (PPh3)2, Cp′ = Cp; PP = dppe, Cp′ = Cp*] were also obtained as minor by-products and synthesised independently from Ru(C≡CC≡CH)(PP)Cp′.
A reaction between Co3{μ3-CC≡CC≡CAu(PPh3)}(μ-dppm)(CO)7 and Ru3(CO)12 afforded {(Ph3P)(OC)9AuRu3}C≡CC≡CC{Co3(μ-dppm)(CO)7} 7. Related complexes AuRu3{μ3-C2C≡[M(CO)2Tp]}(CO)9(PPh3) (M = Mo 8, W 9) were obtained from {Tp(OC)2M}≡CC≡C{Au(PPh3)}, while the mixed metal cluster complexes MoM2(C2Me)(CO)8Tp (M = Ru 13, Fe 14) were obtained from M(≡CC≡CSiMe3)(CO)2Tp (M = Mo, W) with Fe2(CO)9 and Ru3(CO)12, respectively. Reactions of the Mo carbyne complex with Co2(LL)(CO)6 [LL = (CO)2, μ-dppm] or nickelocene afforded complexes 15–17 in which Co2 and Ni2 fragments, respectively, had coordinated to the C≡C triple bond. XRD structural determinations of 7, 8, 14, 16 and {Tp(OC)2W}≡CC≡CC≡{Co3(μ-dppm)(CO)7} (18-W) are reported.
In memoriam: F. Albert Cotton (1930–2007). 相似文献
10.
Mark G. Humphrey Brian W. Skelton Allan H. White Brian F. Yates 《Journal of organometallic chemistry》2005,690(6):1487-1497
Treatment of Ru3(CO)12 with Ph3PS affords the compounds [Ru3(μ3-S)2(CO)9 − n(PPh3)n] (n = 1 (1a), 2 (2a)) and [Ru3(μ3-S)(μ3-CO)(CO)7(PPh3)2] (3a) as the major products. Single crystal X-ray diffraction studies of [Ru3(μ3-S)2(CO)8(PPh3)] and [Ru3(μ3-S)(μ3-CO)(CO)7(PPh3)2] show these two classes of compounds to contain square pyramidal Ru3S2 and trigonal pyramidal Ru3S metal cores, respectively, with the latter being isostructural to the analogous selenide cluster compound. The clusters [Ru3(μ3-E)2(CO)9 − n(PPh3)n] (E = S, n = 1; E = Se, n = 2) readily undergo ligand displacement reactions with PPh3 to afford the compounds [Ru3(μ3-E)2(CO)6(PPh3)3] (E = S, 5a; E = Se 5b). The mixed chalcogenide cluster, [Ru3(μ3-S)(μ3-Se)(CO)7(PPh3)2] (6), was prepared from the reaction of [Ru3(μ3-S)(μ3-CO)(CO)7(PPh3)2] and SePPh3. The optical limiting properties of the complexes 1a,b, 2a,b, 5a,b have been measured by the Z-scan technique employing 40 ns pulses at 523 nm; power limiting was observed for all clusters under our experimental conditions. 相似文献
11.
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
12.
The title compound can be prepared in good yield by heating either [Ru4(μ-H)4(CO)12] or [Au2Ru4(μ3-H)2(CO)12(PPh3)2] with [AuMe(PPh3)] in toluene. The related compound [Au3Ru4(μ3-H)(μ-dppm)(CO)12(PPh3)] has also been prepared. Both trigoldtetraruthenium clusters undergo dynamic behaviour in solution, involving intramolecular rearrangement of the metal core, as revealed by variable temperature NMR studies. The crystal structure of [Au3Ru4(μ3-H)(CO)12(PPh3)3] has been established by an X-ray diffraction study. The metal atom core comprises a trigonal bipyramidal AuRu4 unit with two AuRu2 faces capped by gold atoms. 相似文献
13.
Lindsay T. Byrne George A. Koutsantonis Brian W. Skelton Allan H. White 《Journal of organometallic chemistry》2008,693(10):1738-1750
The trimetallic clusters [Ru3(CO)10(dppm)], [Ru3(CO)12] and [RuCo2(CO)11] react with a number of multifunctional secondary phosphine and tertiary arsine ligands to give products consequent on carbonyl substitution and, in the case of the secondary phosphines, PH activation. The reaction with the unresolved mixed P/S donor, 1-phenylphosphino-2-thio(ethane), HSCH2CH2PHPh ( LH2), gave two products under various conditions which have been characterised by spectroscopic and crystallographic means. These two complexes [Ru3(μ-dppm)(H)(CO)7(LH)] and [Ru3(μ-dppm)(H)(CO)8(LH)Ru3(μ-dppm)(CO)9], show the versatility of the ligand, with it chelating in the former and bridging two Ru3 units in the latter. The stereogenic centres in the molecules gave rise to complicated spectroscopic data which are consistent with the presence of diastereoisomers. In the case of [Ru3(CO)12] the reaction with LH2 gave a poor yield of a tetranuclear butterfly cluster, [Ru4(CO)10(L)2], in which two of the ligands bridge opposite hinge wingtip bonds of the cluster. A related ligand, HSCH2CH2AsMe(C6H4CH2OMe), reacted with [RuCo2(CO)11] to give a low yield of the heterobimetallic Ru-Co adduct, [RuCo(CO)6(SCH2CH2AsMe(C6H4CH2OMe))], which appears to be the only one of its type so far structurally characterised.The secondary phosphine, HPMe(C6H4(CH2OMe)) and its oxide HP(O)Me(C6H4(CH2OMe)) also react with the cluster [Ru3(CO)10(dppm)] to give carbonyl substitution products, [Ru3(CO)5(dppm)(μ2-PMe(C6H4CH2OMe))4], and [Ru3H(CO)7(dppm)(μ2,η1-P(O)Me(C6H4CH2OMe))]. The former consists of an open Ru3 triangle with four phosphide ligands bridging the metal-metal bonds; the latter has the O atom symmetrically bridging one Ru-Ru bond, the P atom being attached to a non-bridged Ru atom. 相似文献
14.
Shishir Ghosh Shariff E. Kabir Ebbe Nordlander Derek A. Tocher 《Journal of organometallic chemistry》2011,696(10):1982-1989
Oxidative-addition of PhTe2Ph to the furyne cluster [Ru3(CO)7(μ-H)(μ3-η2-C4H2O){μ-P(C4H3O)2}(μ-dppm)] (1) results in the isolation of four complexes; (i) the previously reported 54-electron cluster [Ru3(CO)6(μ3-Te)2(μ-TePh)2(μ-dppm)] (5) which results from elimination of trifuryl phosphine, (ii) the furenyl cluster [Ru3(CO)5(μ-η2-C4H3O){μ-P(C4H3O)2}(μ-TePh)2(μ-dppm)] (6) which results from carbon-hydrogen bond formation and (iii) two new 50-electron complexes [Ru3(CO)5(μ-H)(μ3-η2-C4H2O){μ-P(C4H3O)2}(μ-TePh)2(к2-dppm)] (7) and [Ru3(CO)4(μ-H){P(C4H3O)3}(μ3-η2-C4H2O){μ-P(C4H3O)2}(μ-TePh)2(к2-dppm)] (8) both containing unsymmetrical furyne ligands. The structures of all the new compounds have been unambiguously established by single crystal X-ray crystallography. Further reactivity studies have provided a clear understanding of the relative sequence of the key oxidative-addition and reductive-elimination processes, showing that 6 is an intermediate in the formation of 7. DFT calculations have been used to shed light on the unsymmetrical binding of the furyne ligand in 7 and also to show that the adopted position of the heteroatom within the furyne ring can vary within complexes of this type. 相似文献
15.
Shishir Ghosh Kaniz Fatema Md. Rafique Al-Mamun Graeme Hogarth 《Journal of organometallic chemistry》2011,696(18):2935-2942
Reaction of [Mn2(CO)9(NCMe)] with tetrahydropyrimidine-2-thione (thpymSH) at 25 °C furnishes the mono- and dinuclear complexes [Mn(CO)4(κ1:η1-SCNHC3H6NCO)] (2) and [Mn2(CO)6(μ-thpymS)2] (1), respectively. Carbon-nitrogen coupling is observed in compound 2 resulting in the formation of κ1:η1-SCNHC3H6NCO ligand while compound 1 adopts a centrosymmetric structure. Reaction of 1 with [Os3(CO)10(NCMe)2] at 80 °C affords the mixed Mn-Os cluster [MnOs3(CO)13(μ3-thpymS)] (3) which possesses a butterfly skeleton of four metal atoms whereas with Ru3(CO)12 at 110 °C gives the mixed Mn-Ru complex [MnRu3(CO)14(μ4-S)(κ1:η1-thpym)] (4). In contrast, treatment of 1 with Fe3(CO)12 at 80 °C furnishes two triiron complexes [Fe3(CO)9(μ3-S)(μ3-κ1:η1-C4H6N2)] (5) and [Fe3(CO)8(μ3-S)2(η1-C4H8N2)] (6). The former also results from the direct reaction of thpymSH with Fe3(CO)12 and reacts with H2S to afford 6. The molecular structures of all these new complexes have been determined by X-ray diffraction studies. 相似文献
16.
Reaction of the heteronuclear cluster RuOs3(μ-H)2(CO)13 (1) with azulene under thermal activation afforded the novel clusters RuOs3(μ-H)(CO)9(μ3,η5:η2:η2-C10H9) (3) and Ru2Os3(μ-H)2(CO)13(μ-CO)(μ3,η5:σ2-C10H8) (5a), with 4,6,8-trimethylazulene to give RuOs3(μ-H)(CO)8(μ-CO)(μ,η5:η4-C10H6Me3) (4) and Ru2Os3(μ-H)2(CO)13(μ-CO)(μ3,η5:σ2-C10H5Me3) (5b), and with guaiazulene to give Ru2Os3(CO)11(μ3,η5:η3:η3-C10H5Me2iPr) (6), respectively. In 3–5, cluster-to-ligand hydrogen transfer appears to have taken place, with the organic moiety capping a trimetallic face in 3, bridging a metal–metal bond in 4 and via a μ3,η5:σ2 bonding mode in 5a and 5b. Cluster 6 contains a trigonal bipyramidal metal framework with the guaiazulene ligand over a triangular metal face. All five clusters have been completely characterised, including by single-crystal X-ray diffraction analysis. 相似文献
17.
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
18.
A. A. Koridze V. I. Zdanovich V. Yu. Lagunova M. G. Ezernitskaya P. V. Petrovskii F. M. Dolgushin A. I. Yanovsky 《Russian Chemical Bulletin》1998,47(5):988-994
Complex Ru3(μ-CO)2(CO)6{μ3-η1:η1:η4:η4-C4Ph2(CH=CHPh)2} containing an open triruthenium framework undergoes rearrangement to the Ru3-triangular Ru3(CO)8{μ3-η1:η1:η4:η2-C4Ph2(CH=CHPh)2) cluster when heated in refluxing hexane. Reactions of the latter complex with PPh3, P(OPri)3, and CO were studied. The structure of one of the reaction products, the Ru3(CO)8(PPh3{μ3-η1:η1:η4-C4Ph2(CH=CHPh)2} cluster, was established by X-ray structural analysis. 相似文献
19.
Michael P. Brown Susan J. Franklin Richard J. Puddephatt Mary A. Thomson Kenneth R. Seddon 《Journal of organometallic chemistry》1979,178(1):281-290
Reaction of [Pt2Cl2(μ-dppm)2] with ligands, L, in the presence of [PF6- gave stable cationic diplatinum(I) complexes [Pt2L2(μ-dppm)2][PF6]2 where L = PMe2Ph, PMePh2, PPh3, NH3, C5H5N. Reaction of [Pt2(NH3)2(μ-dppm)2][PF6]2 with CO gave [Pt2(CO)2(μ-dppm)2][PF6]2 and an unsymmetrical complex [Pt2(CO)(C5H5N)(μ-dppm)2][PF6]2 was also prepared. The compounds were characterized by vibrational and 1H and 31P NMR spectroscopy and the presence of direct platinumplatinum bonds is indicated. 相似文献
20.
Renato Rosseto 《Journal of organometallic chemistry》2004,689(1):111-121
The synthesis and characterisation of μ3-η2-alkynyl triruthenium clusters, [Ru3(μ3-η2-R1-4-C6H4CCR2)(μ-dppm)(μ-CO)(CO)7] (1, saturated), [Ru3(μ3-η2-R1-4-C6H4CCR2)(μ-dppm)(CO)7] (2, unsaturated) and [Ru3(μ3-η2-R1-4-C6H4CCR2)(μ-dppm)(PPh3)(CO)7] (3, saturated) containing symmetrical and asymmetrical alkynes in which R1 and R2 are electron donor or electron withdrawing groups in the para position of the aromatic ring(s) or R2 is ferrocenyl, are reported. Clusters 1 were obtained from the reactions of [PPN][Ru3(μ-Cl)(CO)10] with R1-4-C6H4CCR2 and dppm. Clusters 1 were successfully decarbonylated to give unsturated clusters 2, with the exception of the FcCCC6H4-4-NO2 containing cluster, which is stable. Novel adducts 3 were obtained in high yields by addition of PPh3 to unsaturated clusters 2. Clusters 1-3 were characterised by analytical and spectroscopic data, and structures were proposed on the basis of systematic 31P NMR studies and correlations with X-ray structural data of related compounds available in the literature. Saturated compounds 1 contain a CO and a dppm ligands bridging the same edge, which is also parallel to the μ3-η2-alkyne, as opposed to the structure previously proposed for the PhCCPh and other derivatives, and established by X-ray crystallography for the PhCCCCPh cluster derivative, in which the dppm ligand bridges a different edge. Unsaturated compounds 2 exhibit the same structure established for the PhCCPh derivative in the solid state, with the alkyne bonded in the μ3-η2-mode perpendicular to the Ru2 edge supported by the dppm ligand. Because the dppm phosphorus chemical shifts were sensitive to the alkyne electronic asymmetry, it was possible to show that clusters containing electronically asymmetrical alkynes exist in two inseparable isomeric forms, which differ with respect to the alkyne orientation. Similarly to their osmium analogues, saturated compounds 3 exist as inseparable mixtures of isomers that differ with respect to the position of the bridging CO and dppm ligands, and in the cases of asymmetrical alkyne derivatives, also with respect to the orientation of the alkyne. This work has established, therefore, that μ-CO and dppm ligand positions respective to the μ3-η2-alkyne in saturated clusters 1 and 3 are sensitive both to the nature of the coordinated alkyne and to the presence of a PPh3 in place of a CO ligand on the metal frame. 相似文献