The heteronuclear cluster RuOs3(μ-H)2(CO)13—a high yield synthesis, isomerism and a triphenylphosphine derivative

Pereira, Leonard Joachim; Leong, Weng Kee; Wong, Siew Heng

doi:10.1016/s0022-328x(00)00134-0

Cited by 27 publications

(25 citation statements)

References 15 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…These lines lie in 2θ values between those observed for the thin films obtained from the homometallic clusters Os 3 (CO) 12 (5) and Ru 3 (CO) 12 (6), which were also polycrystalline with a preferred (002) orientation (Fig. S2).…”

Section: Deposition Of An Os-ru Alloy Thin Film Using a Single-sourcementioning

confidence: 52%

“…The clusters Os 2 (CO) 6 (µ-I) 2 (2), [10] Os 3 (CO) 12 Br 2 (3) [11] and RuOs 3 (CO) 13 (µ-H) 2 (4) [12] were prepared according to reported procedures. The compounds Os 3 (CO) 12 (5) and Ru 3 (CO) 12 (6) were purchased from Oxkem Ltd and used as supplied.…”

Section: Methodsmentioning

confidence: 99%

“…[1] Osmium has a number of applications, for example, in the fabrication of gate material for high-k dielectrics, methane-detection chemical sensors, X-ray mask materials, thermionic cathodes and in the making of conductive coatings with good secondary electron emission efficiency. [2] In recent years, osmium or osmium oxide thin films with reasonable purity have been obtained from Os(C 5 H 5 ) 2 , [3] OsO 4 , [4] Os(CO) 5 , [5] Os 3 (CO) 12 , [6] Os(CO) 4 (CF 3 C CCF 3 ), [7] cis-Os(CO) 4 I 2 , fac-Os(CO) 3 [OC(COCF 3 ) 2 ](O 2 CCF 3 ), [8] [Os(CO) 3 {3, 5-(CF 3 ) 2 -pz}] 2 and Os 3 (CO) 10 (µ-H) [3, ) 2 -pz] (pz = pyrazole). [9] Since osmium clusters are air-stable at room temperature and have sufficient volatility to be transported in the vapor phase, they make possible precursors for the deposition of osmium thin films.…”

Section: Introductionmentioning

confidence: 99%

“…(1), Os 2 (CO) 6 (µ-I) 2 (2) and Os 3 (CO) 12 Br 2 (3) as precursors for the deposition of osmium thin films, as well as the heteronuclear carbonyl cluster RuOs 3 (CO) 13 (µ-H) 2 (4) to form an Os-Ru alloy thin film (Fig. 1).…”

Section: Introductionmentioning

confidence: 99%

See 3 more Smart Citations

Deposition of osmium and ruthenium thin films from organometallic cluster precursors

Leong

2009

Applied Organom Chemis

Self Cite

View full text Add to dashboard Cite

show abstract

Section: Deposition Of An Os-ru Alloy Thin Film Using a Single-sourcementioning

confidence: 52%

Section: Methodsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

Deposition of osmium and ruthenium thin films from organometallic cluster precursors

Leong

2009

Applied Organom Chemis

Self Cite

View full text Add to dashboard Cite

show abstract

“…This is in contrast with the results of Pereira et al who obtained an 1:2 mixture of osmium-and ruthenium-substituted isomers after the reaction of PPh 3 with the tetranuclear mixed-metal cluster [RuOs 3 (μ-H) 2 -(CO) 13 ] under similar conditions. [34] The geometry around the phosphorus atom in cluster 2 is essentially tetrahedral, the phenyl groups being slightly bent away from the Ru atom [C-P-C angles are in the range 100.30 (13) [32] ]. This is partly due to the substitution of a π-accepting CO ligand by the much stronger σ-donor PPh 3 , increasing the electron density on the metal core and resulting in expansion.…”

Section: Molecular Structure Of [Os 2 Ru(co) 11 (Pph 3 )] (2)mentioning

confidence: 99%

Heterosite Effects in Novel Heteronuclear Clusters [Os₂Ru(CO)₁₁(PPh₃)] and [Os₂Ru(CO)₁₀(2‐acetylpyridine‐N‐isopropylimine)]

et al. 2005

View full text Add to dashboard Cite

A new synthetic route towards the mixed-metal cluster [Os 2 -Ru(CO) 12 ] is described together with the syntheses of its PPh 3 and iPr-AcPy (iPr-AcPy = 2-acetylpyridine-N-isopropylimine) derivatives. The molecular structures of the novel clusters [Os 2 Ru(CO) 11 (PPh 3 )] and [Os 2 Ru(CO) 10 (iPr-AcPy)] were determined on the basis of crystalline solid solutions of the Os 2 Ru and corresponding Os 3 species. The structures reveal that coordination of the Lewis bases occurs exclusively at the ruthenium site of [Os 2 Ru(CO) 12 ], which is in agreement with density functional theory (DFT) calculations on several structural isomers of these compounds. According to the time-dependent DFT results, the lowest optically accessible excited state of [Os 2 Ru(CO) 10 (iPr-AcPy)] has a prevailing σ(Ru-Os2)-π*(iPr-AcPy) character, with a partial σσ*(Ru-Os2) contribution. In weakly coordinating 2-chlorobutane, the excited state has a lifetime τ = 10.4 ± 1.2 ps and produces biradicals considerably faster than observed for [Os 3 (CO) 10 (iPr-AcPy) (τ = 25.3 ± 0.7 ps). In coordinating acetonitrile, the excited state of [Os 2 Ru(CO) 10 (iPr-AcPy)] decays mono-exponentially with a lifetime τ = 2.1 ± 0.2 ps. In contrast to [Os 3 (CO) 10 (iPr-AcPy)]

show abstract

Drastic Acceleration of Phosphine/Phosphite Incorporation into a Tetrahydrido Ruthenium/Osmium Complex, and One‐way Ruthenium to Osmium Migration of a Phosphorus Ligand

2008

View full text Add to dashboard Cite

Cluster complexes form an attractive class in the reactions of transition metal complexes, owing to their capability of activating substrates effectively through the cooperative effects of multiple metal centers. [1] To date, we have demonstrated several examples of cooperative activation by treating various substrates, including unsaturated hydrocarbons, with [Cp*Ru(m-H) 4 RuCp*] (1, Cp* = h 5 -C 5 Me 5 ) and [(Cp*Ru) 3 (m-H) 3 (m 3 -H) 2 ]. [2] Heterometallic cluster complexes that contain different metals may exhibit electronic anisotropic characters stemming from polarized metal-metal bonds. [3] Therefore, significant heterometallic effects, such as marked regioselectivity and remarkable acceleration, could occur in the reaction in addition to the typical effects of cluster complexes resulting from multiple coordination and multielectron transfer.We synthesized a series of heterometallic dinuclear polyhydrido complexes, such as [Cp*Ru(m-H) 4 and demonstrated their heterometallic effects through reactions with unsaturated hydrocarbons, phosphines, amines, and acetylacetone. For example, the reaction of heterometallic Ru-Os complex [Cp*Ru(m-H) 4 OsCp*] (2) with ethylene exclusively afforded [Cp*Os(CH 2 = CH 2 )(m-h 1 ,h 2 -CH = CH 2 ) 2 RuCp*] in which the vinyl groups are h 1 -bonded to Os. [4a] In this reaction, CÀH bond activation selectively occurred at the Os center because Os and Ru atoms served as activation and binding sites, respectively, indicating sharing of functions between the two metal atoms in the reactions of the heterometallic dinuclear polyhydrido clusters. However, the aforementioned reactions, particularly reactions with unsaturated hydrocarbons, involved multiple elementary steps, and the complexity of the reaction often obscured the heterometallic effect in each elementary step. To evaluate the heterometallic effect, this study focused on the addition of a phosphorus ligand to the dinuclear tetrahydrido complex [Cp*M(m-H) 4 M'Cp*] (2: M = Ru, M' = Os; 3: M = M' = Os [5] ) to produce a dihydrido-phosphine or dihydrido-phosphite complex [Cp*(X 3 P)M(m-H) 2 M'Cp*] (X = OMe, Me). Through these reactions, we obtained positive evidence for a kinetic heterometallic effect (KHE) and a thermodynamic heterometallic effect (THE), namely, remarkable acceleration of the incorporation of phosphine or phosphite groups into the heterodinuclear tetrahydride 2 and intramolecular migration of P(OMe) 3 from the ruthenium center to the osmium center in one direction in [Cp*{(MeO) 3 P}Ru(m-H) 2 OsH 2 Cp*] (4), respectively. We have reported the formation of dinuclear dihydridophosphine and dihydrido-phosphite complexes [Cp*-(R 3 P)Ru(m-H) 2 RuCp*] (R = Me (5 a), Et (5 b), iPr (5 c), Bn (5 d), OMe (5 e), and OPh (5 f)) in the reaction of diruthenium tetrahydrido complex 1 with various phosphorus ligands [Eq. ( 1)]. We also demonstrated that the phosphorus ligand reversibly migrated between the two ruthenium atoms. [6] Similarly, diosmium tetrahydrido complex 3 reacted with P(OMe) 3 to generate a dinuclear phos...

show abstract

The heteronuclear cluster RuOs3(μ-H)2(CO)13—a high yield synthesis, isomerism and a triphenylphosphine derivative

Cited by 27 publications

References 15 publications

Deposition of osmium and ruthenium thin films from organometallic cluster precursors

Deposition of osmium and ruthenium thin films from organometallic cluster precursors

Heterosite Effects in Novel Heteronuclear Clusters [Os₂Ru(CO)₁₁(PPh₃)] and [Os₂Ru(CO)₁₀(2‐acetylpyridine‐N‐isopropylimine)]

Drastic Acceleration of Phosphine/Phosphite Incorporation into a Tetrahydrido Ruthenium/Osmium Complex, and One‐way Ruthenium to Osmium Migration of a Phosphorus Ligand

Contact Info

Product

Resources

About

The heteronuclear cluster RuOs3(μ-H)2(CO)13—a high yield synthesis, isomerism and a triphenylphosphine derivative

Cited by 27 publications

References 15 publications

Deposition of osmium and ruthenium thin films from organometallic cluster precursors

Deposition of osmium and ruthenium thin films from organometallic cluster precursors

Heterosite Effects in Novel Heteronuclear Clusters [Os2Ru(CO)11(PPh3)] and [Os2Ru(CO)10(2‐acetylpyridine‐N‐isopropylimine)]

Drastic Acceleration of Phosphine/Phosphite Incorporation into a Tetrahydrido Ruthenium/Osmium Complex, and One‐way Ruthenium to Osmium Migration of a Phosphorus Ligand

Contact Info

Product

Resources

About

Heterosite Effects in Novel Heteronuclear Clusters [Os₂Ru(CO)₁₁(PPh₃)] and [Os₂Ru(CO)₁₀(2‐acetylpyridine‐N‐isopropylimine)]