Reaction of the heteronuclear cluster RuOs3(μ-H)2(CO)13 with toluene

The heteronuclear cluster RuOs₃(μ-H)₂(CO)₁₃ (4) reacts with refluxing toluene to form the clusters Ru₂Os₃(μ-H)₂(CO)₁₆ (5) RuOs₃(CO)₉(μ-CO)₂(η⁶-C₆H₅Me) (6) and Ru₂Os₃(CO)₁₂(μ-CO)(η⁶-C₆H₅Me) (7). Cluster 5 exists as a mixture of five isomers. The inter-relationship among the clusters has also been investigated.     

Reactivity of the heteronuclear cluster RuOs3(μ-H)2(CO)13 with indene

The heteronuclear cluster RuOs₃(μ-H)₂(CO)₁₃ (1) reacts with indene under thermal activation to afford the novel clusters RuOs₃(μ-H)(CO)₉(μ-CO)₂(η⁵-C₉H₇) (3), RuOs₃(μ-H)(CO)₉(μ₃,η⁵:η²:η²-C₉H₇) (4) and Ru₂Os₃(μ-H)(CO)₁₁(μ₃,η⁵:η²:η²-C₉H₇) (5), the latter two possessing indenyl ligands in the μ₃,η⁵:η²:η² bonding mode. Cluster 5 exists as a mixture of two isomers. The inter-relationship among the clusters has also been investigated.     

Synthesis, structure and electrochemistry of CO incorporated diruthenium metallacyclic compounds [Ru2(CO)6{μ-η:η:η:η-1,4-Fc2C5H2O}] and [Ru2(CO)6{μ-η:η:η:η-1,5-Fc2C5H2O}]

Ferrocenyl substituted ruthenium metallacyclic compounds, [Ru₂(CO)₆{μ-η¹:η¹:η²:η²-1,4-Fc₂C₅H₂O}] (1) and [Ru₂(CO)₆{μ-η¹:η¹:η²:η²-1,5-Fc₂C₅H₂O}] (2) have been synthesized and structurally characterized. Electrochemical studies for 1 and 2 and the respective quinone derivatives 3 and 4 show weak to no electrochemical coupling at the mixed-valent intermediate state which is dependent on the complex frameworks.     

Trimetallic ReBiPt complexes containing spiro-bismuth ligands from the reaction of the bis(tri-t-butylphosphine)platinum with Re3(CO)12(μ-BiPh2)(μ-H)2

Pt(P-t-Bu₃)₂ reacts with the bismuthtrirhenium complex Re₃(CO)₁₂(μ-BiPh₂)(μ-H)₂, 1 at 68 °C to give eight complexes PtRe₂(CO)₉P(t-Bu₃)(μ-H)₂, 2, PtRe₃(CO)₁₂P(t-Bu₃)(μ-Ph)(μ-H)(μ₄-Bi), 3, PtRe₃(CO)₁₃P(t-Bu₃)(μ₄-Bi)(μ-H)₂, 4, PtRe₄(CO)₁₆P(t-Bu₃)(μ-H)₂(μ₄-Bi)(μ₃-Bi), 5, Pt₂Re₅(CO)₂₁[P(t-Bu)₃]₂(μ-H)₃(μ₄-Bi)₂, 6, trans-Pt₂Re₅(CO)₂₂[P(t-Bu)₃]₂(μ-H)₃(μ₄-Bi)_2,trans-7, cis-Pt₂Re₅(CO)₂₂[P(t-Bu)₃]₂(μ-H)₃(μ₄-Bi)₂, cis-7, (an isomer of trans-7) and Re₃(CO)₁₃[PtPBu^t₃]₂(μ-H)₂(μ₄-Bi), 8, all in low yields. When 4 was treated with Pt(P-t-Bu₃)₂ at 68 °C, compounds 2, trans-7, cis-7, and Pt₂Re₄(CO)₁₈[P(t-Bu)₃]₂(μ-H)₂(μ₄-Bi)₂, 9 were formed. When 8 was treated with CO at 25 °C, compounds 2, trans-7, 9, and PtRe₃(CO)₉P(t-Bu)₃(μ₃-Bi)(μ₄-Bi₂), 10 were formed. In all of the products both of the phenyl rings from the bridging BiPh₂ ligand of 1 were cleaved from the bismuth atom. Only compound 3 contains a phenyl ligand and that ligand was a bridging ligand across the Pt-Re bond. All of the products, except 10, and the known compound 2, contain spiro, μ₄-Bi ligands. The higher nuclearity complexes 5, 6, trans-7, cis-7, and 9 contain two bismuth ligands. Compound 10 contains three bismuth atoms. Two of the bismuth atoms in 10 are part of an octahedrally-shaped Re₃PtBi₂ cluster. The third bismuth atom is a triply-bridging ligand on the triangular Re₃ face of the cluster. When a mixture of 4 and 8 was heated to 68 °C in the presence of CO, the new compound PtRe₄(CO)₁₇(P-t-Bu₃)(μ-H)₂(μ₄-Bi), 11 was formed. The molecular structures of all of the new complexes were characterized by single-crystal X-ray diffraction analyses.     

簇合物Co3(CO)7(μ3-S)[μ,η2-CNP(S)(C6H4OCH3)OC(Ph)CH]和Co3(CO)7(μ3-S)[μ,η2-SCNC(CH3)2P(S)(Cl)N(Ph)]的合成与晶体结构

用Co₂(CO)₈分别与两个杂环配体C(S)NHP(S)(C₆H₄OCH₃)OC(Ph)CH (L₁)和C(S)NHC(CH₃)₂P(S)(Cl)N(Ph) (L₂)反应,合成两个新的三核钴羰基硫簇合物Co₃(CO)₇(μ₃-S)[μ,η²-CNP(S)(C₆H₄OCH₃)OC(Ph)CH](Ⅰ)和Co₃(CO)₇(μ₃-S)[μ,η²-SCNC(CH₃)₂P(S)(Cl)N(Ph)](Ⅱ)。用元素分析,IR, ¹H NMR, ³¹P NMR及MS谱表征了它们的结构,同时用X射线衍射法测定了它们的晶体分子结构,二者属于三斜晶系,空间群P1,Ⅰ的晶胞参数为:a=0.84768(1)nm,b=1.19049(3)nm,c=1.43639(1)nm,α=86.926(1)°,β=81.601(3)°,γ=88.535(2)°,V=1.4318(5)nm³,Z=2,D_c=1.641g·cm^-3,F(000)=716,μ=1.893mm^-1,R=0.0602,R_w=0.1515。Ⅱ的晶胞参数为:a=1.2050(2)nm,b=1.2448(2)nm,c=0.8951(2)nm,α=97.49(1)°,β=93.552(4)°,γ=108.432(3)°,V=1.2554(3)nm³,Z=2,D_c=1.841g·cm^-3,F(000)=690,μ=2.419mm^-1,R=0.0423,R_w=0.1075。Ⅰ和Ⅱ的分子骨架Co3S为三角锥构型,S作为面桥基配体,所有CO作为端基配体与三个Co原子成键。Ⅰ中含有CoCoCN四元环组件,Ⅱ中含有CoCoSCN五元环组件。     

Synthesis of Mo(CO)2(η-PPh2(o-C6H4)C(O)H)2 and its reaction with C60

Reaction of Mo(CO)₃(NCMe)₃ and PPh₂(o-C₆H₄)C(O)H (abbreviated as PCHO) at room temperature affords Mo(CO)₂(η³-PCHO)₂ (1), while compound 1 and the phosphine-imine complex Mo(CO)₄(η²-PPh₂(o-C₆H₄)CHNMe) (2) are obtained by using Mo(CO)₃(η³-(MeNCH₂)₃) as the reactant. Thermal reaction of 1 with C₆₀ products Mo(CO)₂(η⁴-(PPh₂(o-C₆H₄)CH)₂)(η²-C₆₀) (3) in low yield, apparently through coupling of the formyl moieties. The structures of 1 and 3 have been determined by an X-ray diffraction study. The two aldehyde groups of 1 and C₆₀ ligand of 3 are coordinated to the molybdenum atom in a π-fashion.     

Synthesis and reaction chemistry of [(μ-SeR)(μ-σ,π-CCPh)]Fe2(CO)6

RSeCCPh (1a, R = Et; 1b, R = n-Bu; 1c, R = Ph; 1d, R = 2,4,6-Me₃C₆H₂) reacts with equimolar amounts of Fe₂(CO)₉ (2) to give [(μ-SeR)(μ-σ,π-CCPh)]Fe₂(CO)₆ (3a, R = Et; 3b, R = n-Bu; 3c, R = Ph; 3d, R = 2,4,6-Me₃C₆H₂).Complexes 3a-3d exist as two isomers, depending on the axial or equatorial position of R at selenium.Addition of P(OⁱC₃H₇)₃ (4) to 3d affords {(μ-Se-2,4,6-Me₃C₆H₂)[μ-η¹-CCPh(P(OⁱC₃H₇)₃)]}Fe₂(CO)₆ (5) along with {(μ-Se-2,4,6-Me₃C₆H₂)[μ-η¹:η¹-PhCC(P(OⁱC₃H₇)₃)]}Fe₂(CO)₆ (6).The solid-state structures of 3d, 5 and 6 were determined by single X-ray structure analysis.In mononuclear 3d the Fe(CO)₃ fragments are bridged by a μ-Se-2,4,6-Me₃C₆H₂ and a μ-σ,π-CCPh unit, resulting in an over-all butterfly arrangement.Due to steric reasons, the mesityl group is pointing away from the PhCC entity and hence, is located in an equatorial position.Compounds 5 and 6, which co-crystallise in the ratio of 7:93, feature aμ-bridging 2,4,6-Me₃C₆H₂Se unit and either a vinylidenic CCPh(P(OⁱC₃H₇)₃) (complex 5) or a olefinic PhCC(P(OⁱC₃H₇)₃) (complex 6) building block of which the latter entity is part of a diiron cyclobutene ring.     

Formation of the silylene-bridged complex Fe2(CO)6(μ2-SiCl2)3 from cis-Fe(CO)4(SiCl3)2: an experimental and computational study

Abstract  

Thermolysis of cis-Fe(CO)₄(SiCl₃)₂ results in the formation of the novel compound Fe₂(CO)₆(μ₂-SiCl₂)₃, which was characterized by single crystal X-ray diffraction. Density functional theory calculations were carried out to elucidate possible reaction steps leading to the formation of Fe₂(CO)₆(SiCl₂)₃, including CO dissociation and chlorine abstraction by a SiCl₃ radical generated from homolytic Fe–Si bond cleavage involving a singlet–triplet intersystem crossing.     

Regiospecific insertion into the Co–Co bond of the mixed-metal cluster Co2Rh2(CO)12 by an electron-poor alkyne: X-ray diffraction structure of the butterfly cluster Co2Rh2(CO)10(μ-HCCCO2Me)

The reaction between the mixed-metal tetrahedral cluster Co₂Rh₂(CO)₁₂ (1) and the electron-poor alkyne methyl propiolate in hexane at room temperature furnishes a mixture of products consisting of Co₃Rh(CO)₁₂ (2), Co₃Rh(CO)₁₀(μ-HCCCO₂Me) (3), Co₂Rh₂(CO)₁₀(μ-HCCCO₂Me) (4), and CoRh₃(CO)₉(μ-HCCCO₂Me)₃ (5). The isolation and solution spectroscopic data of these compounds are described, and the solid-state structure of Co₂Rh₂(CO)₁₀(μ-HCCCO₂Me) determined by X-ray diffraction analysis. The title cluster crystallizes in the triclinic space group. The solid-state structure of Co₂Rh₂(CO)₁₀(μ-HCCCO₂Me) provides proof for the regiospecific insertion of the methyl propiolate ligand into the Co–Co bond of the starting cluster Co₂Rh₂(CO)₁₂. The stability of clusters 3 and 4 in the presence of added methyl propiolate is discussed.     

Reactions of Ru3(CO)12 with 2-pentynal-diethyl-acetal. The crystal structure of Ru2(CO)6[μ-η-{EtC2C(H)(OEt)2}CO{EtC2C(H)(OEt)2}] and its reactivity towards tetraethyl-orthosilicate

The title compound has been obtained in considerable yield by reacting Ru₃(CO)₁₂ with 2-pentynal-diethyl-acetal [CH₃CH₂CCC(H)(OEt)₂] (PDA) in hydrocarbon solvents. The X-ray analysis shows that the title complex belongs to the well known family of the flyover derivatives. Some X-ray structural studies have been reported, many years ago, on di-iron flyover complexes; in contrast only a few examples of diruthenium derivatives have been structurally characterized.The complex contains ethoxy-groups which could potentially undergo hydrolysis in the presence of tetraethyl-orthosilicate (TEOS) in the presence of catalysts. Reactions of complex Ru₂(CO)₆[μ-η⁴-{EtC₂C(H)(OEt)₂}CO{EtC₂C(H)(OEt)₂}] with TEOS in the presence of HCl or of NaF (as catalysts) have been attempted. An inorganic-organometallic sol-gel material containing the skeleton of the complex has been obtained and characterized with IR-Raman, XRD on powders and SEM microscopy.     

Synthesis and structures of the silyl bridged bis(indenyl) diruthenium complexes and a novel indenyl nonanuclear ruthenium cluster Ru9(μ6-C)(CO)14(μ3-η:η:η-C9H7)2

Thermal treatment of C₉H₇SiMe₂C₉H₇ and C₉H₇Me₂SiOSiMe₂C₉H₇ with Ru₃(CO)₁₂ in refluxing xylene gave the corresponding diruthenium complexes (E)[(η⁵-C₉H₆)Ru(CO)]₂(μ-CO)₂ [E = Me₂Si (1), Me₂SiOSiMe₂ (2)]. A desilylation product [(η⁵-C₉H₇)Ru(CO)]₂(μ-CO)₂ (3) was also obtained in the latter case. Similar treatment of C₉H₇Me₂SiSiMe₂C₉H₇ with Ru₃(CO)₁₂ gave a novel indenyl nonanuclear ruthenium cluster Ru₉(μ₆-C)(CO)₁₄(μ₃-η⁵:η²:η²-C₉H₇)₂ (5) with carbon-centered tricapped trigonal prism geometry, in addition to the diruthenium complex (Me₂SiSiMe₂)[(η⁵-C₉H₆)Ru(CO)]₂(μ-CO)₂ (4) and the desilylation product 3. Complex 4 can undergo a thermal rearrangement to form the product [(Me₂Si)(η⁵-C₉H₆)Ru(CO)₂]₂ (6). The molecular structures of 1, 2, 4, 5, and 6 were determined by X-ray diffraction.     

Synthesis and molecular structures of the Co3(μ-OOCPh)4(μ,η2-OOCPh)2[OC(Ph)OHNEt3]2 and Co(Hdmpz)2(OOCPh)2 complexes (Hdmpz = 3,5-dimethylpyrazole)

The product of the thermal reaction between cobalt acetate hydrate and benzoic acid reacts with a triethylamine excess to form the trinuclear complex Co₃(μ-OOCPh)₄(μ,η²-OOCPh)₂[OC(Ph)OHNEt₃]₂, and its reaction with 3,5-dimethylpyrazole yields the mononuclear complex Co(Hdmpz)₂(OOCPh)₂. The compound structures are discussed on the basis of X-ray crystallographic data.     

Photochemical reactions of W(CO)6 with hydrosilanes: synthesis, spectroscopic characteristic, and crystal structure of W(CO)3(η-PhSiHPh2)

Photolysis of W(CO)₆ in the presence of Ph₃SiH in n-heptane leads to the formation of the first tricarbonyl(η⁶-triphenylhydrosilane)tungsten complex W(CO)₃(η⁶-PhSiHPh₂) (1) in good yield (ca. 70%). The molecular structure of the new tungsten-silane compound was established by single-crystal X-ray diffraction studies and characterized by IR, UV-Vis, ¹H, ¹³C{¹H}, and ²⁹Si{¹H} NMR spectroscopy.     

Ditertiary phosphine derivatives of the heteronuclear cluster RuOs3(μ-H)2(CO)13

The heteronuclear cluster RuOs₃(μ-H)₂(CO)₁₃ (1) reacted readily with a number of ditertiary phosphines under chemical activation with trimethylamine-N-oxide. The solid-state and solution structures of these derivatives have been examined. Six structural types have been characterized crystallographically, including one in which a phenyl group migrates from the ditertiary phosphine ligand to the metal framework. There are many more isomers present in solution, most of which are rapidly inter-converting via hydride migrations.     

The reaction of Ru3(CO)12 with 1,4-dichloro-but-2-yne in basic methanolic solution. Synthesis and crystal structure of (μ-H)2Ru3(CO)9{μ3-η-[H2CC(H)CCC(O)OCH3]}

The title complex is obtained by reacting Ru₃(CO)₁₂ with 1,4-dichloro-but-2-yne (ClCH₂CCCH₂Cl, DCB) in CH₃OH/KOH solution (followed by acidification with HCl). The X-ray structure analysis shows that (μ-H)₂Ru₃(CO)₉{μ₃-η²-[H₂CC(H)CCC(O)OCH₃]} complex contains a “parallel” ene-yne acetyl substituent, H₂CC(H)CCC(O)OCH₃; the formation of such a ligand starting from DCB is - to our knowledge - unprecedented. The synthesis of complex (μ-H)₂Ru₃(CO)₉{μ₃-η²-[H₂CC(H)CCC(O)OCH₃]} occurs through the activation of CO and methanol. This process has been found for other reactions of functionalized alkynes with M₃(CO)₁₂ carbonyls (M = Fe, Ru) under basic methanolic conditions.The known hydridic cluster, (μ-H)Ru₃(CO)₉[μ₃-η³-(MeCCHCH)] has been identified as the minor reaction product.     

Carbon-carbon coupling on tetrahedral iridium clusters: X-ray molecular structures and multinuclear NMR studies of the two isomeric forms of [Ir4(CO)6(μ3-η-HCCPh)(μ2-η-C4H2Ph2)(μ-PPh2)2]

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.     

Reactions of linked tetrahedron clusters [Co2(CO)6(μ-HC2CH2O)-]2R with Rh2(CO)4Cl2 to give mixed-metal linked alkyne-bridged butterfly clusters containing C2Co2Rh2 unit

The reactions of compound Rh₂(CO)₄Cl₂, 1 with [Co₂(CO)₆(μ-HC₂CH₂O)-]₂R (R = C₆H₄, 2; (COCH₂)₂, 3; C₆H₄-1,4-(CO)₂, 4; (COCH)₂, 5; (CO)₂, 6) in benzene at 60 °C produce five new mixed-metal linked clusters Rh₂Co₂(CO)₁₀(μ₄,η²-HC₂CH₂O-R-OCH₂C₂H-μ)Co₂(CO)₆ (R = C₆H₄, 7a; (COCH₂)₂, 7b; C₆H₄-1,4-(CO)₂, 7c; (COCH)₂, 7d; (CO)₂, 7e) and five known linked octahedral clusters [Rh₂Co₂(CO)₁₀(μ₄,η²-HC₂CH₂O-)]₂R (R = C₆H₄, 8a; (COCH₂)₂, 8b; C₆H₄-1,4-(CO)₂, 8c; (COCH)₂, 8d; (CO)₂, 8e), respectively. Treatment of clusters 7a-8e in benzene at room temperature under air for 24 h with stirring afford the precursor clusters 2-6, respectively. The structure of cluster 7a has been determined by single-crystal X-ray diffraction. The linked cluster 7apossesses two isomers A and B in its structures, the Rh₂(CO)₄ unit inserts into one of two Co-Co bonds and coordinates to the Co₂C₂ core forming one distorted closo-Rh₂Co₂C₂ octahedron framework which is connected to the Co₂C₂ tetrahedron unit via C₆H₄(OCH₂)₂-1,4 as a bridging ligand. All clusters were characterized by C, H elemental analysis, IR and ¹H NMR spectroscopy.     

对苯二甲酸二丙炔醇酯与Co2(CO)8、Mo2Cp2(CO)4和RuCo2(CO)11的反应

室温下对苯二甲酸二丙炔醇酯分别与Co2CO8Mo2Cp2CO4和RuCo2CO11反应得到三个有机金属化合物C6H4pCO2CH2C2Hμ2Co2CO621、C6H4pCO2CH2C2H2RuCo2CO922和HC2CH2OCOC6H4pCO2CH2C2HμMo2Cp2CO43。研究发现三种金属核对端炔氢的屏蔽作用依次为RuCo2CO9>Co2CO6>Mo2CO4Cp2。化合物1的晶体衍射发现属三斜晶系空间群a=8.1392b=8.8083c=11.3433β=96.2606°V=773.443Z=1Dc=1.748g·cm-3R=0.0513wR=0.1266。     

Nitrosyl derivatives of the unsaturated dihydrides [Mn2(μ-H)2(CO)6(μ-L2)] (L2 = Ph2PCH2PPh2, (EtO)2POP(OEt)2)

The title dimanganese complexes react with NO (5% in N₂) at room temperature to give as major products the corresponding hexanitrosyl derivatives [Mn₂(NO)₆(μ-L₂)] in moderate yields, and they react rapidly with NO₂ to give the corresponding hydride derivatives [Mn₂(μ-H)(μ-NO₂)(CO)₆(μ-L₂)], these having a nitrite ligand bridging the dimetal centre through the N and O atoms. The dppm-bridged dihydride also reacts selectively at 273 K with (PPN)NO₂ to give first the nitro derivative (PPN)[Mn₂(μ-H)(H)(NO₂)(CO)₆(μ-dppm)], which then transforms into the nitrosyl complex (PPN)[Mn₂(μ-CO)(CO)₅(NO)(μ-dppm)] at room temperature or above (dppm = Ph₂PCH₂PPh₂; PPN⁺ = [N(PPh₃)₂]⁺). The latter anion reacts with (NH₄)PF₆ to give the hydride-bridged nitrosyl complex [Mn₂(μ-H)(μ-NO)(CO)₆(μ-dppm)] and with [AuCl(PPh₃)] to give the trinuclear cluster [AuMn₂(μ-NO)(CO)₆(μ-dppm)(PPh₃)] (Mn-Au = ca. 2.68 Å; Mn-Mn = 2.879(2) Å). Both products are derived from the addition of the added electrophile at the intermetallic bond and rearrangement of the nitrosyl ligand into a bridging position. In contrast, methylation of the anion with CF₃SO₃Me takes place at the nitrosyl ligand to yield the unstable methoxylimide derivative [Mn₂(μ-NOMe)(CO)₆(μ-dppm)]. Analogous reactions at the nitrosyl ligand take place upon the addition of HBF₄·OEt₂ to the nitrosyl-bridged hydrides [Mn₂(μ-H)(μ-NO)(CO)_n(μ-dppm)_m] (n = 6, m = 1; n = 4, m = 2) to give the corresponding hydroxylimide derivatives [Mn₂(μ-H)(μ-NOH)(CO)_n(μ-dppm)_m]BF₄, which were also thermally unstable and could not be isolated nor fully characterized.