Diruthenium tetracarbonyl sawhorse complexes bearing N-heterocylic carbene and phosphine ligands: Synthesis, structural characterization, and catalytic activity

Rohrabaugh, Thomas N.; Doverspike, Joshua C.; Geib, Steven J.; Sawyer, Evan D.; Stibbard, Mitchell R.; Malosh, Thomas J.

doi:10.1016/j.jorganchem.2015.11.006

Journal of Organometallic Chemistry

2016

DOI: 10.1016/j.jorganchem.2015.11.006

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Diruthenium tetracarbonyl sawhorse complexes bearing N-heterocylic carbene and phosphine ligands: Synthesis, structural characterization, and catalytic activity

Thomas N. Rohrabaugh

Joshua C. Doverspike

Steven J. Geib

et al.

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Cited by 4 publications

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“…Tris(pentafluorophenyl)phosphine (TPFPP) has been widely used as a ligand to construct catalysts. − The solid-state structure of TPFPP (TPFPP-I) was first documented in 1986 and reported in the literature 3 years later . TPFPP-I crystallizes in the monoclinic system, space group P 2 1 / c , from ethyl alcohol with one TPFPP molecule in the asymmetric unit cell.…”

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confidence: 99%

“Useless Channels” in a Molecular Crystal Formed via F···F and F···π Halogen Bonds

Yuan

et al. 2022

Crystal Growth & Design

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Tris(pentafluorophenyl)phosphine molecules in a new phase pack to form hourglass-shaped one-dimensional channels, whose inner surface is occupied by only fluorine. The channels show an effective diameter of 3.80 Å at the belly and only 2.68 Å at the neck, neither being possible for the encapsulation of any solvent molecules or for the permeability of air (N2 and O2), thus demonstrating an absolute vacuum. Such “vacuum” channels in the crystals have never been reported and would be of great significance in photo- and electrophysics. In addition, the structural analysis indicated that F···F contacts and F···π interactions are mainly responsible for the specific packing in the new phase, and a σ-hole-type attraction is found in both F···F and F···π forces according to the DFT computations.

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mentioning

confidence: 99%

“Useless Channels” in a Molecular Crystal Formed via F···F and F···π Halogen Bonds

Yuan

et al. 2022

Crystal Growth & Design

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The Thermolysis of Ru₃(CO)₁₂ with Carboxylic Acids Revisited: Stepwise Assembly of Ru₂ to Ru₆ Cluster Frameworks

et al. 2016

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Thermolysis of Ru 3 (CO) 12 with carboxylic acids directly accessed a large variety of low valence ruthenium carbonyl complexs. Under the conditions of the reaction firstly reported by J. Lewis, 3 equivalents of acids were employed to assembly sawhorsetype dirutheniumtetra carbonyl complex. Six Ru 3 -Ru 6 ruthenium clusters were unexpectedly isolated in the reaction of Ru 3 (CO) 12 with 1 equivalent of carboxylic acids under thermal condition. The reaction of Ru 3 (CO) 12 with ten kind of carboxylic acids were systematically investigated. The reactions of Ru 3 (CO) 12 with non-coordinative carboxylic acids afforded b-H 2 Ru 4 (CO) 13 (2), Ru 6 (m 6 -C)(m-CO)(CO) 16 (3) and then to Ru 6 (m 6 -C)(m-CO)(CO) 13 (h 6 -C 6 H 5 CH 3 ) (4), respectively. The further experiments indicated that the formation of 3 was attributed to the assembly of tetraruthenium carbonyl dihydrid 2 with polymeric sawhorse diruthenium intermediate [Ru 2 (CO) 4 (OOR) 2 ] n (R = alkyl, aryl). The thermolysis of phenylpropiolic acid with Ru 3 (CO) 12 unveiled an alternative pathway to access Ru 6 skeleton. The triruthenium cluster [(m-H)Ru 3 (CO) 9 (m 3 -h 2 -(?)-C CC 6 H 5 )] (5) and butterfly tetraruthenium compound Ru 4 (CO) 12 (HC CC 6 H 5 ) (6) were identified as the key intermediates in the construction of compound 3.[a] J.

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Synthesis, Characterization, and Crystal Structures of Diruthenium Complexes Containing Bridging Salicylato Ligands

Jiang

Yau

et al. 2017

Z. Anorg. Allg. Chem.

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The thermal reaction of Ru 3 (CO) 12 (1) with salicylic acid, in the presence of triphenylphosphine, pyridine, or dimethylsulfoxide, afforded the dinuclear complexes Ru 2 (CO) 4 (μ-O 2 CC 6 H 4 OH) 2 L 2 (2) [L = PPh 3 (2a). C 5 H 5 N (2b); (CH 3 ) 2 SO (2c)]. Complex 2b was further reacted with the aromatic dimmines 2,2Ј-dipyridine or 1,10-phenanthroline to give the cationic diruthenium complexes [Ru 2 (CO) 2 878 CO) 2 (μ-O 2 CC 6 H 4 OH)(NʝN) 2 ] + (3) [(NʝN) = 2,2Ј-dipyridine (3a); 1,10-phenanthroline (3b)], which were isolated as their tetraphenylborate salts. All five novel complexes were characterized spectroscopically and analytically . For 2a-2b and 3a-3b, single-crystal X-ray diffraction studies were also carried out.

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Diruthenium tetracarbonyl sawhorse complexes bearing N-heterocylic carbene and phosphine ligands: Synthesis, structural characterization, and catalytic activity

Cited by 4 publications

References 41 publications

“Useless Channels” in a Molecular Crystal Formed via F···F and F···π Halogen Bonds

“Useless Channels” in a Molecular Crystal Formed via F···F and F···π Halogen Bonds

The Thermolysis of Ru₃(CO)₁₂ with Carboxylic Acids Revisited: Stepwise Assembly of Ru₂ to Ru₆ Cluster Frameworks

Synthesis, Characterization, and Crystal Structures of Diruthenium Complexes Containing Bridging Salicylato Ligands

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Diruthenium tetracarbonyl sawhorse complexes bearing N-heterocylic carbene and phosphine ligands: Synthesis, structural characterization, and catalytic activity

Cited by 4 publications

References 41 publications

“Useless Channels” in a Molecular Crystal Formed via F···F and F···π Halogen Bonds

“Useless Channels” in a Molecular Crystal Formed via F···F and F···π Halogen Bonds

The Thermolysis of Ru3(CO)12 with Carboxylic Acids Revisited: Stepwise Assembly of Ru2 to Ru6 Cluster Frameworks

Synthesis, Characterization, and Crystal Structures of Diruthenium Complexes Containing Bridging Salicylato Ligands

Contact Info

Product

Resources

About

The Thermolysis of Ru₃(CO)₁₂ with Carboxylic Acids Revisited: Stepwise Assembly of Ru₂ to Ru₆ Cluster Frameworks