Synthesis, characterization, crystal structures and reactivity of a series of ruthenium nitrene and nitrido carbonyl clusters containing bridging alkyne ligands

Ho, Emmie N.M.; Wong, Wing Tak

doi:10.1039/a806091f

Cited by 18 publications

(46 citation statements)

References 24 publications

(19 reference statements)

Supporting

Mentioning

Contrasting

Order By: Relevance

“…[13,48] In comparison with the electron-precise cluster 4, the chemical shifts of 6 and the tetraruthenium µ 4 -NH clusters appear further upfield. Diamagnetic effects had previously been observed in the 1 H and 15 N chemical shifts of the µ 4 -NH groups in 6 and [Ru 4 (CO) 9 (µ-CO) 2 (µ 4 -NH)(µ 4 -η 2 -PhC 2 Ph)].…”

Section: Thermolysis Of 2 With Phc 2 Phmentioning

confidence: 98%

“…In the UV/vis spectrum of 6, absorption bands are seen at 296, 330, 420, and 505 nm. [13,14] The Cp* ligands are coordinated to the Co atoms at distances of 1.687 and 1.722 Å in 6 and 7, respectively. Detailed assignments of the protons of the diphenylacetylene ligands were made with the aid of a 2D HH-COSY experiment (see Table 1).…”

Section: Thermolysis Of 2 With Phc 2 Phmentioning

confidence: 99%

“…[13] Thus, an Ru(CO) 3 or an RuCo(CO) 5 fragment is eliminated to give a more favourable metal framework, i.e. The only other known example occurs in [Ru 6 (CO) 13 (µ-H)(µ 5 -N)(µ 3 -η 2 -PhC 2 Ph) 2 ].…”

Section: Reaction Of [Ru 3 Co(co) 12 (µ 4 -N)] With [Cp*co(co) 2 ]mentioning

confidence: 99%

“…The redox potential values obtained are summarized in Table 7; for comparison, those of compounds [Ru 4 (CO) 9 (µ-CO) 2 (11) are also listed. Electrochemical data for compounds 1؊3, 6, 8, and [Ru 4 (CO) 9 (µ-CO) 2 (µ 4 -NR)(µ 4 -η 2 -PhC 2 Ph)] [9, R ϭ OMe; 10, R ϭ H, and 11, R ϭ C(O)OMe] [13] Cluster [a] Oxidation The cluster [Ru 3 (CO) 9 (µ 3 -CO)(µ 3 -NOMe)] exhibits an irreversible cathodic wave (E pc ) at Ϫ1.66 V vs. Ag/AgNO 3 , along with a weak oxidation wave at Ϫ0.63 V. The region where the weak oxidation wave appears was initially empty, with the wave appearing after the cathodic wave was traversed. Electrochemical data for compounds 1؊3, 6, 8, and [Ru 4 (CO) 9 (µ-CO) 2 (µ 4 -NR)(µ 4 -η 2 -PhC 2 Ph)] [9, R ϭ OMe; 10, R ϭ H, and 11, R ϭ C(O)OMe] [13] Cluster [a] Oxidation The cluster [Ru 3 (CO) 9 (µ 3 -CO)(µ 3 -NOMe)] exhibits an irreversible cathodic wave (E pc ) at Ϫ1.66 V vs. Ag/AgNO 3 , along with a weak oxidation wave at Ϫ0.63 V. The region where the weak oxidation wave appears was initially empty, with the wave appearing after the cathodic wave was traversed.…”

Section: Electrochemistrymentioning

confidence: 99%

“…A series of nitrene clusters containing alkyne ligands, [Ru 4 (CO) 9 (µ-CO) 2 (µ 4 -NR)(µ 4 -η 2 -PhC 2 RЈ)] [R ϭ H, OMe, or C(O)OMe; RЈ ϭ H or Ph], was obtained in more acceptable yields from reactions of [Ru 3 (CO) 9 (µ 3 -CO)(µ 3 -NOMe)] with alkynes. [13,14] It is suspected that the formation of nitrido ligands, and hence of nitrene ligands as well, involves initial NϪO bond scission of the methoxynitrido ligand. In the formation of these polynuclear µ 4nitrido or µ 4 -NR species, coupling reactions of the methoxynitrido clusters such as [Ru 3 (CO) 9 (µ 3 -CO)(µ 3 -NOMe)] or 1 with other organometallic moieties (another molecule of a methoxynitrido cluster or some degraded ruthenium carbonyl fragments) is invariably accompanied by NϪO bond cleavage.…”

Section: Introductionmentioning

confidence: 99%

See 4 more Smart Citations

Ruthenium−Cobalt Mixed-Metal Nitrido and Nitrene Carbonyl Clusters: Structure, Reactivity, and15N NMR Spectroscopy

Lin

Wong

2001

Eur. J. Inorg. Chem.

Self Cite

View full text Add to dashboard Cite

The reaction of [Ru3(μ‐H)2(CO)9(μ3‐NOMe)] (1) with [Cp*Co(CO)2] (Cp* = η5‐C5Me5) in refluxing THF afforded the new clusters [Ru3Co(μ‐H)(CO)9(η5‐C5Me5)(μ4‐N)] (2), [Ru2Co(CO)6(μ3‐CO)(η5‐C5Me5)(μ3‐NH)] (3), [Ru5(μ‐H)(CO)9(μ‐CO)3(η5‐C5Me5)(μ4‐NH)] (4), and [Ru6Co(μ3‐H)(CO)8(μ‐CO)3(μ4‐η2‐CO)(η5‐C5Me5)3(μ4‐N)] (5). Clusters 2 and 3 have typical butterfly nitrido and triangular nitrene structures, whilst compound 4 is a novel square‐pyramidal pentaruthenium μ4‐NH carbonyl cluster with a Cp* ligand transferred from the external mononuclear Co complex. Cluster 4 can also be obtained by the reaction of 1 with pentamethylcyclopentadiene in the presence of 1,3‐cyclohexadiene, albeit in low yield. Compound 5 consists of a rare Ru6Co metal framework where a basal Ru−Ru edge of the central Ru4 tetrahedron is capped by a Cp*Co fragment and another edge is bridged by a diruthenium unit. Complex 2 was found to be converted into 3 upon deprotonation with 1,8‐diazabicyclo[5.4.0]undec‐7‐ene, on refluxing with [Cp*Co(CO)2], or on exhaustive electrolysis. Upon thermolysis of 2 with PhC2Ph in n‐octane, [Ru3Co(CO)6(μ‐CO)2(η5‐C5Me5)(μ4‐NH)(μ4‐η2‐PhC2Ph)] (6) and [Ru3Co(CO)5(μ‐CO)2(η5‐C5Me5){μ4‐η3‐NC(O)C2(C4H4)CHCH(Ph)}(μ4‐η2‐PhC2Ph)] (7) were obtained in moderate yields. The structures of 6 and 7 both consist of a slightly twisted Ru3Co square base with a quadruply bridging PhC2Ph ligand. Cluster 6 is capped by a μ4‐NH moiety on the opposite side, while in 7 a CO ligand and an ortho‐carbon atom of a Ph group from another PhC2Ph ligand interact with the μ4‐N nitrido atom. Molecular orbital calculations have been carried out in order to gain further insight into the electronic structures of these interesting square‐planar Ru3Co and Ru4 clusters. The butterfly Ru2Co2 nitrido complex [Ru2Co2(CO)9(η5‐C5Me5)(μ4‐N)] (8) was isolated from the reaction of [Ru3Co(CO)12(μ4‐N)] with [Cp*Co(CO)2] in refluxing THF as a result of metal exchange of an Ru(CO)3 fragment by a Cp*Co moiety. The redox properties of the compounds described herein have been investigated by means of cyclic voltammetry and controlled potential coulometry. Cluster 6 was shown to be able to tolerate both the addition of two electrons and the removal of one electron without significant structural change. The chemical environments of the nitrogen atoms of these clusters have been investigated by analysis of their 15N NMR chemical shifts.

show abstract

Section: Thermolysis Of 2 With Phc 2 Phmentioning

confidence: 98%

Section: Thermolysis Of 2 With Phc 2 Phmentioning

confidence: 99%

Section: Reaction Of [Ru 3 Co(co) 12 (µ 4 -N)] With [Cp*co(co) 2 ]mentioning

confidence: 99%

Section: Electrochemistrymentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 3 more Smart Citations

Ruthenium−Cobalt Mixed-Metal Nitrido and Nitrene Carbonyl Clusters: Structure, Reactivity, and15N NMR Spectroscopy

Lin

Wong

2001

Eur. J. Inorg. Chem.

Self Cite

View full text Add to dashboard Cite

show abstract

Synthesis, Characterisation, Crystal Structures, Reactivity, and Electrochemistry of Ruthenium-Nitrido, Ruthenium-Cobalt-Imido and Ruthenapyrrolidone Carbonyl Clusters Containing Alkyne Ligands

Lin

Wong

2001

Chem. Eur. J.

Self Cite

View full text Add to dashboard Cite

Thermolysis of [Ru3(CO)9(mu3-NOMe)(mu3-eta2-PhC2Ph)] (1) with two equivalents of [Cp*Co(CO)2] in THF afforded four new clusters, brown [Ru5(CO)8(mu-CO)3(eta5-C5Me5)(mu5-N)(mu4-eta2-PhC2Ph)] (2), green [Ru3Co2(CO)7(mu3-CO)(eta5-C5Me5)2(mu3-NH)[mu4-eta8-C6H4-C(H)C(Ph)]] (3), orange [Ru3(CO)7(mu-eta6-C5Me4CH2)[mu-eta3-PhC2(Ph)C(O)N(OMe)]] (4) and pale yellow [Ru2(CO)6[mu-eta3-PhC2(Ph)C(O)N(OMe)]] (5). Cluster 2 is a pentaruthenium mu5-nitrido complex, in which the five metal atoms are arranged in a novel "spiked" square-planar metal skeleton with a quadruply bridging alkyne ligand. The mu5-nitrido N atom exhibits an unusually low frequency chemical shift in its 15N NMR spectrum. Cluster 3 contains a triangular Ru2Co-imido moiety linked to a ruthenium-cobaltocene through the mu4-eta8-C6H4C(H)C(Ph) ligand. Clusters 4 and 5 are both metallapyrrolidone complexes, in which interaction of diphenylacetylene with CO and the NOMe nitrene moiety were observed. In 4, one methyl group of the Cp* ring is activated and interacts with a ruthenium atom. The "distorted" Ru3Co butterfly nitrido complex [Ru3Co(CO)5(eta5-C5Me5)(mu4-N)(mu3-eta2-PhC2Ph)(mu-I)2I] (6) was isolated from the reaction of 1 with [Cp*Co(CO)I2] heated under reflux in THF, in which a Ru-Ru wing edge is missing. Two bridging and one terminal iodides were found to be placed along the two Ru-Ru wing edges and at a hinge Ru atom, respectively. The redox properties of the selected compounds in this study were investigated by using cyclic voltammetry and controlled potential coulometry. 15N magnetic resonance spectroscopy studies were also performed on these clusters.

show abstract

Dinuclear Ru/Os Compounds with Metal–Metal Bonds

Wilton‐Ely

2007

Comprehensive Organometallic Chemistry III

View full text Add to dashboard Cite

Synthesis, characterization, crystal structures and reactivity of a series of ruthenium nitrene and nitrido carbonyl clusters containing bridging alkyne ligands

Cited by 18 publications

References 24 publications

Ruthenium−Cobalt Mixed-Metal Nitrido and Nitrene Carbonyl Clusters: Structure, Reactivity, and15N NMR Spectroscopy

Ruthenium−Cobalt Mixed-Metal Nitrido and Nitrene Carbonyl Clusters: Structure, Reactivity, and15N NMR Spectroscopy

Synthesis, Characterisation, Crystal Structures, Reactivity, and Electrochemistry of Ruthenium-Nitrido, Ruthenium-Cobalt-Imido and Ruthenapyrrolidone Carbonyl Clusters Containing Alkyne Ligands

Dinuclear Ru/Os Compounds with Metal–Metal Bonds

Contact Info

Product

Resources

About