X-ray crystal structures of Ru3(μ-H)(μ-C,N-C5H4N)(CO)10-n (P i Pr3) n ,n=0,1: A A case of the hydride following the Phosphine?

Ellis, David; Farrugia, Louis J.

doi:10.1007/bf01166177

Cited by 12 publications

(6 citation statements)

References 21 publications

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“…Although the N atoms of the ligand are attached to the Ru 3 triangle in an analogous way as that found in many triruthenium clusters containing apy ligands, ,,, a comparison of the Ru−C and Ru−N bond distances involving the abq ligand in 1 with analogous bond distances in related cluster complexes indicates that, as a consequence of the structure and the rigidity of the bridging ligand, the cluster is rather constrained. Thus, while the Ru−C metalated distance, 2.116(8) Å, is similar to other Ru−C distances involving metalated rings, 2a,, the Ru−N amido distances are ca. 0.04−0.10 Å shorter than those of μ 3 -apy-bridged Ru 3 clusters. ,, …”

Section: Resultssupporting

confidence: 50%

“…Compounds 1 and 2 are unique, not only because they are the first polynuclear derivatives of H 2 abq but also because of their structures. Metalated heterocyclic ligands tend to occupy axial positions in trinuclear clusters; ,− in other words, they are positioned on one side of the metal triangle. However, the particular structure of the abq ligand and its coordination through three atoms (two nitrogens and one carbon) forces the occupation of both axial and equatorial positions in complex 1 and a completely new type of structure for complex 2 .…”

Section: Discussionmentioning

confidence: 99%

“…However, the particular structure of the abq ligand and its coordination through three atoms (two nitrogens and one carbon) forces the occupation of both axial and equatorial positions in complex 1 and a completely new type of structure for complex 2 . In the reported cases where two cyclometalated pyridine or quinoline ligands have been incorporated into a trinuclear cluster, both ligands occupy axial positions on either sides of the metal triangle. 8f,14b However, in complex 2 , both abq ligands are cut by the Ru 3 plane, resulting in an uncommon structure for which no axial or equatorial sites can be proposed.…”

Section: Discussionmentioning

confidence: 99%

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Triruthenium and Triosmium Carbonyl Cluster Complexes Containing Bridging Ligands Derived from 2-Amino-7,8-benzoquinoline

et al. 2002

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The ruthenium cluster complexes [Ru3(μ3-η3-abq-C,N,N)(CO)9] (1) and [Ru3(μ-H)2(μ3-η3-abq-C,N,N)2(CO)6] (2) (H2abq = 2-amino-7,8-benzoquinoline) have been stepwise prepared from [Ru3(CO)10(MeCN)2]. Both compounds contain cyclometalated abq ligands which span a Ru−Ru edge through the N atom of an amido fragment and chelate the remaining Ru atom through both the quinolinic N atom and the C atom of the cyclometalated ring. For steric reasons, the cyclometalation is responsible for the observation of short Ru−Namido bond lengths. The reaction of the osmium cluster [Os3(CO)10(MeCN)2] with H2abq gives the amido-bridged decacarbonyl derivative [Os3(μ-Η)(μ-η1-Habq-N)(CO)10] (3). Curiously, while complex 3 is stable in refluxing toluene, the ruthenium analogue of 3 has not been detected. Compounds 1−3 represent the first trinuclear carbonyl clusters containing ligands derived from 2-amino-7,8-benzoquinoline.

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Section: Resultssupporting

confidence: 50%

Section: Discussionmentioning

confidence: 99%

Section: Discussionmentioning

confidence: 99%

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Triruthenium and Triosmium Carbonyl Cluster Complexes Containing Bridging Ligands Derived from 2-Amino-7,8-benzoquinoline

et al. 2002

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“…This carbonyl ligand appears to derive from our starting alcohol, by analogy to an iridium-based alcohol oxidation system that we have recently characterized . While the ortho-metalated pyridyl fragment is a common substructure in ruthenium carbonyl clusters, − typically derived from Ru 3 (CO) 12 , complex 4 is a unique example of tandem selective monocarbonylation, pyridine ortho-metalation, and cluster self-assembly all happening from a mononuclear precursor.…”

Section: Resultsmentioning

confidence: 99%

Catalyst Evolution in Ruthenium-Catalyzed Coupling of Amines and Alcohols

Cherepakhin

Williams

2019

ACS Catal.

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We describe the mechanism, scope, and catalyst evolution for our ruthenium-based coupling of amines and alcohols, which proceeds from a [(η6-cymene)RuCl(PyCH2P t Bu2)]OTf (1) precatalyst. The method selectively produces secondary amines through a hydrogen borrowing mechanism and is successfully applied to several heterocyclic carbinol substrates. Under the reaction conditions, precatalyst 1 evolves through a series of catalytic intermediates: [(η6-cymene)RuH(PyCH2P t Bu2)]OTf (3), [Ru3H2Cl2(CO)(PyCH2P t Bu2)2{μ-(C5H3N)CH2P t Bu2}]OTf (4), and a diastereomeric pair of [Ru2HCl(CO)2(PyCH2P t Bu2)2(μ-O2C n Pr)]X (trans-5, X = Cl; cis-6, X = OTf). The structures of 4 and 6 were established by single-crystal X-ray diffraction. A study of catalytic activity shows that 4 is a dormant (but alive) form of the catalyst, whereas 5 and 6 are the ultimate dead forms. Electrochemical studies show that 4 is redox active and undergoes electrochemically reversible one-electron oxidation at E 1/2 = 0.442 V (vs Fc+/Fc) in CH2Cl2 solution. We discuss the factors that govern the formation of 3–6 and the role of selective ruthenium carbonylation, which is essential for enabling generation of the active catalyst. We also connect these discoveries to the identification of conditions for amination of aliphatic alcohols, which eluded us until we understood the catalyst’s complex speciation behavior.

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“…The metalation of pyridine rings has been reported on a few occasions . However, it is noteworthy that the coordination mode of the metalated dpa ligand in complex 1 is very rare.…”

Section: Discussionmentioning

confidence: 99%

Triruthenium and Triosmium Carbonyl Cluster Complexes Containing Deprotonated Di(2-pyridyl)amine in Unusual Coordination Modes

et al. 2002

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The synthesis of the first trinuclear carbonyl clusters containing ligands derived from di(2-pyridyl)amine (Hdpa) has been achieved. Treatment of [Ru3(CO)12] or [Ru3(CO)10(MeCN)2] with di(2-pyridyl)amine (Hdpa) gives the cluster complex [Ru3(μ-Η)(μ-η3-dpa-C,N,N)(CO)9] (1). The dpa ligand in this compound chelates a Ru atom through both pyridinic nitrogens while attached to another Ru atom through the C atom of a metalated pyridine ring, keeping the amino NH fragment uncoordinated. Curiously, the osmium compounds [Os3(μ-Η)(μ-η2-dpa-N,N)(CO)10] (2) and [Os3(μ-Η)(μ3-η2-dpa-N,N)(CO)9] (3), which have been stepwise prepared from [Os3(CO)10(MeCN)2] and Hdpa, contain edge-bridging (2) and face-capping (3) N-deprotonated dpa ligands coordinated through the N atom of a pyridine ring and the N atom of the original amino fragment.

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X-ray crystal structures of Ru3(μ-H)(μ-C,N-C5H4N)(CO)10-n (P i Pr3) n ,n=0,1: A A case of the hydride following the Phosphine?

Cited by 12 publications

References 21 publications

Triruthenium and Triosmium Carbonyl Cluster Complexes Containing Bridging Ligands Derived from 2-Amino-7,8-benzoquinoline

Triruthenium and Triosmium Carbonyl Cluster Complexes Containing Bridging Ligands Derived from 2-Amino-7,8-benzoquinoline

Catalyst Evolution in Ruthenium-Catalyzed Coupling of Amines and Alcohols

Triruthenium and Triosmium Carbonyl Cluster Complexes Containing Deprotonated Di(2-pyridyl)amine in Unusual Coordination Modes

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