Synthesis and Properties of a Triruthenium Hydrido Complex Capped by a μ<sub>3</sub>-Oxoboryl Ligand

Kaneko, Takeshi; Ninagawa, Hayato; Matsuoka, Moe; Takao, Toshiro

doi:10.1021/acs.organomet.9b00182

Cited by 3 publications

(4 citation statements)

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“…Similarly, the average C–S bond distance of 1.785 Å in the methanedithiolate unit of 4 is within the single-bond distance. , The 1 H chemical shift at δ 2.84 ppm and a resonance at δ 40.3 ppm in the 13 C{ 1 H} NMR spectrum confirm the presence of a methanedithiolate ligand in 4 . The Ru–Ru bond distance of 2.6388(10) Å in 4 is significantly shorter in comparison to the ruthenium oxo-boryl species [{Cp*Ru(μ-H)} 3 (μ 3 -BO)(μ 3 -H)] (average 2.7162 Å) . This shortening of bond length may be due to the presence of two bridging S atoms that bring the two ruthenium centers closer together, forming acute angles with them.…”

Section: Results and Discussionmentioning

confidence: 94%

“…2.7162 Å). 24 This shortening of bond length may be due to the presence of two bridging S atoms that bring the two ruthenium centers closer forming acute angles with them. The average Ru-B bond distance of 2.152 Å is comparatively shorter as compared to [{Cp*Ru(µ-HBS2CH2-κ 2 B:κ 2 S)}2] 15 (2.185 Å).…”

Section: Hydroboration Of Phenyl Acetylene Using Arachno-[(cp*ru)2b3h8(cs2h)]mentioning

confidence: 99%

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Synthesis, Structure, and Bonding of Bimetallic Bridging Borylene and Boryl Complexes

et al. 2020

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New synthetic route for the synthesis of diruthenium boryl complexes has been established. Thermolysis of an arachno-ruthenaborane, [(Cp*Ru)2B3H8( CS2H)] (1) (Cp* = η 5 -C5Me5) with phenyl acetylene, led to the formation of bridging boryl borylene complex as [(Cp*Ru)2(µ-HBS2CH2-κ 2 B:κ 2 S){µ-B(C6H4)C(CH3)-κ 2 B:κ 2 C}] (2). In parallel to the formation of 2, the reaction also yielded [(Cp*Ru)(μ-H)BH{HC=C(H)Ph}{SC(H)S}] (3a) and [(Cp*Ru)(μ-H)BH( PhC=CH2){SC(H)S}] (3b). To understand the reaction pathways for the formation of 2, we have thermolyzed 1 in toluene that afforded ruthenium bridging bis(boryl) complex, [(Cp*Ru)2(µ-HBS2CH2-κ 2 B:κ 2 S){µ,η 2 :η 2 -SBH}] (4) along with nido-ruthenathiaborane [(Cp*Ru)2(Me)-(S2B2H3)] (5). Nido-5 is structurally and electronically similar with nido-[(Cp + Ru)2( S2C2Ph2)] (Cp + = η 5 -C5Me4Et), which can be generated from the room temperature reaction of [(Cp + Ru)2(μ,η 1 :η 1 -S2)(μ,η 2 :η 2 -S2)] with diphenylacetylene. Thus, nido-5 can be defined as a true mimic of organometallic cluster nido-[(Cp + Ru)2(S2C2Ph2)]. Complex [(Cp*Ru)2(μ,η 1 :η 1 -S2)(μ,η 2 :η 2 -S2)] ( 6) the Cp* analogue of [(Cp + Ru)2(μ,η 1 :η 1 -S2)(μ,η 2 :η 2 -S2)], can be isolated from the reaction of Li[BH2S3] with [Cp*RuCl2]2 along with a diruthenium boryl complex, [(Cp*Ru)2(μ,η 1 :η 1 -S2)(μ-S2BH-κ 1 B:κ 2 S:κ 2 Sʹ)] (7) in which the boryl unit (S2BH) possesses no bulky heterocyclic ligand. Theoretical studies were performed to shed light on the bonding of these borylene and boryl complexes. The theoretical calculations reveal that the stability of these complexes is due to the strong interaction between the borylene and boryl unit with the ruthenium centers.4, 5, 6 and 7. This material is available free of charge via the internet at http://pubs.acs.org.

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Section: Results and Discussionmentioning

confidence: 94%

Section: Hydroboration Of Phenyl Acetylene Using Arachno-[(cp*ru)2b3h8(cs2h)]mentioning

confidence: 99%

Synthesis, Structure, and Bonding of Bimetallic Bridging Borylene and Boryl Complexes

et al. 2020

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“…31 It then isomerized to 5 via 1,2-shift of hydrogen. The lower reactivity of 1 is likely owing to the lack of a μ 3 -hydride, which reduces the mobility of the hydride ligands 47 and increases the barrier of the insertion step of benzonitrile.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

Reaction of a Triruthenium μ₃-Borylene Complex with Benzonitrile: Formation of a μ₃-η³-BCN Ring on a Cationic Ru₃ Plane via Photo-Induced Intramolecular Borylene Transfer

Kaneko

Takao

2020

Organometallics

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A μ 3 -η 2 (||)-iminobenzoyl complex supported by a μ 3 -borylene ligand, [(Cp*Ru) 3 (μ 3 -BH)(μ 3 -η 2 -PhCNH)(μ-H) 2 ] (5a; Cp* = η 5 -C 5 Me 5 ), was synthesized as an equilibrated mixture with its isomer, 5b, by the reaction of a μ 3 -borylene complex, [{Cp*Ru(μ-H)} 3 (μ 3 -BH)] (1), with benzonitrile. Although the structure of 5a is very similar to that of the previously reported μ 3 - 2), the reactivity of 5a is different from that of 2. While the thermolysis of 2 resulted in the reductive elimination of dihydrogen, a μ 3 -2-amino-2-boraruthenacyclopentenyl complex, [{Cp*Ru(μ-H)} 2 {Cp*Ru(−C 6 H 4 −CH-BNH 2 −)}] (6), was obtained by the thermolysis of 5a at 140 °C without hydrogen elimination. In contrast, a cationic μ 3 -η 2 (||)-iminobenzoyl complex, [(Cp*Ru) 3 (μ 3 -BH)(μ 3 -η 2 -PhCNH)(μ-H) 3 ] + (9), which was obtained by the protonation of 5a, showed reactivity similar to that of 2. Irradiation of 10 at a wavelength of 436 nm induced an intramolecular borylene transfer to the μ 3 -η 2 (||)-iminobenzoyl moiety and a cationic complex containing a μ 3 -η 3 -BCN ring, [{Cp*Ru(μ-H)} 3 {μ 3 -η 3 -B(H)N(H)C(Ph)−}] + (10), was obtained. The crystal structure of 10 showed long B−N (1.634(6) Å) and B−C (1.719(6) Å) bonds in the μ 3 -η 3 -BCN skeleton, which are consistent with the small bond indices of 0.539 and 0.433, respectively, and suggest the unsupported nature of these bonds. Time-dependent density functional theory calculations of 2, 5a, and 9 suggested the importance of a μ-hydride at the Ru−Ru edge where the borylene ligand migrates upon irradiation.

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“…Despite the presence of a bulky Cp ‡ group in the cluster skeleton, the Ru–Ru lengths in 1b (Ru(1)–Ru(2) 2.7647(7) Å, Ru(3)–Ru(1) 2.7605(6) Å, and Ru(2)–Ru(3) 2.7498(7) Å) are very similar to those of 1a (2.7453–2.7534 Å). Although the positions of hydrides could not be determined, the similarity in the Ru–Ru lengths implies that 1b possesses the hydrides in the same positions as 1a , specifically three μ- and two μ 3 -hydrides . Although the formal oxidation states of the three ruthenium atoms are likely assigned to Ru(II, III, III), the Ru(1)-Cen1 (1.81 Å), Ru(2)-Cen2 (1.80 Å), and Ru(3)-Cen3 (1.80 Å) distances display almost the same values.…”

Section: Resultsmentioning

confidence: 99%

Selective Synthesis of a Triruthenium Pentahydrido Complex with Mixed-Cp Ligands (C₅^tBu₃H₂ and C₅Me₅) and Its Transformation into Face-Capping Benzene Complexes: Fluxionality of a Face-Capping Benzene Ligand Induced by Oxidation

et al. 2019

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A mixed-ligand triruthenium μ-chloro complex, [(Cp‡Ru)(Cp*Ru)2(μ-H)4(μ-Cl)] (7; Cp‡ = η5-C5 t Bu3H2, Cp* = η5-C5Me5) was synthesized by the reaction of [{Cp*Ru(μ-H)2}2] (5a) with [{Cp‡Ru(μ-Cl)}2] (6). The subsequent treatment of 7 with 2-propanol and a base resulted in the replacement of the μ-Cl ligand by a hydride and afforded a mixed-ligand triruthenium pentahydrido complex, [(Cp‡Ru)(Cp*Ru)2(μ-H)3(μ3-H)2] (1b), which is the analogue of the D 3h symmetrical [{Cp*Ru(μ-H)}3(μ3-H)2] (1a). The pseudo C s symmetrical Ru3 skeletons of 1b and 7 supported by one Cp‡ and two Cp* were unambiguously confirmed by X-ray diffraction. The Ru3 skeleton of 1b promoted the evaluation of the mobility of a face-capping benzene ligand in [(Cp‡Ru)(Cp*Ru)2(μ-H)3(μ3-η2:η2:η2-C6H6)] (2b), which was prepared by the reaction of 1b with 1,3-cyclohexadiene or benzene. Unlike previously reported face-capping benzene complexes, in which the μ3-η2:η2:η2-C6H6 ligand rotates rapidly on the trinuclear plane, the variable-temperature NMR study showed that the face-capping benzene in 2b does not rotate on the Ru3 plane even at 80 °C. This was likely due to the electron-rich nature of the Ru3 site, which strongly binds the benzene ligand. In contrast, the μ3-η3:η3-C6H6 ligand in [(Cp‡Ru)(Cp*Ru)2(μ-H)3(μ3-η3:η3-C6H6)]2+ (4b), obtained by the two-electron oxidation of 2b, rotated rapidly due to the reduced back-donation from the dicationic Ru3 site.

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Synthesis and Properties of a Triruthenium Hydrido Complex Capped by a μ₃-Oxoboryl Ligand

Cited by 3 publications

References 36 publications

Synthesis, Structure, and Bonding of Bimetallic Bridging Borylene and Boryl Complexes

Synthesis, Structure, and Bonding of Bimetallic Bridging Borylene and Boryl Complexes

Reaction of a Triruthenium μ₃-Borylene Complex with Benzonitrile: Formation of a μ₃-η³-BCN Ring on a Cationic Ru₃ Plane via Photo-Induced Intramolecular Borylene Transfer

Selective Synthesis of a Triruthenium Pentahydrido Complex with Mixed-Cp Ligands (C₅^tBu₃H₂ and C₅Me₅) and Its Transformation into Face-Capping Benzene Complexes: Fluxionality of a Face-Capping Benzene Ligand Induced by Oxidation

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Synthesis and Properties of a Triruthenium Hydrido Complex Capped by a μ3-Oxoboryl Ligand

Cited by 3 publications

References 36 publications

Synthesis, Structure, and Bonding of Bimetallic Bridging Borylene and Boryl Complexes

Synthesis, Structure, and Bonding of Bimetallic Bridging Borylene and Boryl Complexes

Reaction of a Triruthenium μ3-Borylene Complex with Benzonitrile: Formation of a μ3-η3-BCN Ring on a Cationic Ru3 Plane via Photo-Induced Intramolecular Borylene Transfer

Selective Synthesis of a Triruthenium Pentahydrido Complex with Mixed-Cp Ligands (C5tBu3H2 and C5Me5) and Its Transformation into Face-Capping Benzene Complexes: Fluxionality of a Face-Capping Benzene Ligand Induced by Oxidation

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Synthesis and Properties of a Triruthenium Hydrido Complex Capped by a μ₃-Oxoboryl Ligand

Reaction of a Triruthenium μ₃-Borylene Complex with Benzonitrile: Formation of a μ₃-η³-BCN Ring on a Cationic Ru₃ Plane via Photo-Induced Intramolecular Borylene Transfer

Selective Synthesis of a Triruthenium Pentahydrido Complex with Mixed-Cp Ligands (C₅^tBu₃H₂ and C₅Me₅) and Its Transformation into Face-Capping Benzene Complexes: Fluxionality of a Face-Capping Benzene Ligand Induced by Oxidation