Formation of Stable<i>trans</i>-Dihydride Ruthenium(II) and 16-Electron Ruthenium(0) Complexes Based on Phosphinite PONOP Pincer Ligands. Reactivity toward Water and Electrophiles

Salem, Hiyam; Shimon, Linda J. W.; Diskin‐Posner, Yael; Leitus, Gregory; Ben‐David, Yehoshoa; Milstein, David

doi:10.1021/om9004077

Cited by 88 publications

(62 citation statements)

References 62 publications

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“…Similar shifts have recently been reported by Milstein et al for trans-dihydridoruthenium complexes containing PONOP pincer ligands. [19] The minor by-product observed in the synthesis of 2 featured a hydride resonance of -16.24 ppm and two sets of Me signals in the 1 H NMR spectrum, indicating the reduced symmetry of this complex. The 13 C{ 1 H} spectrum revealed a shift of 200.9 ppm for the carbene C atom, an identical value as for cationic 3.…”

Section: Spectroscopic Characterizationmentioning

confidence: 95%

Neutral and Cationic Hydridoruthenium Tetrakiscarbene Complexes

2010

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Starting from the novel chlorido precursor trans‐[RuCl2(IMe)4] (1, IMe = 1,3,4,5‐tetramethylimidazol‐2‐ylidene), hydridoruthenium complexes trans‐[RuH2(IMe)4] (2) and [RuH(IMe)4][BEt4] (3BEt4) have been synthesized. Complex 2 was isolated from the reaction of 1 with LiAlH4, while ionic compound 3 was obtained when LiBHEt3 was used as the hydride source. Complexes 1–3 have been characterized by X‐ray crystallography, multinuclear NMR, IR, UV/Vis spectroscopy and mass spectrometry. Neutral dihydride 2 displays a tetragonal bipyramidal geometry with four carbene groups coordinated to ruthenium in equatorial positions and two apical hydrogen atoms. DFT calculations suggest that the trans structure observed for 2 is preferred over a cis arrangement for steric reasons. The ruthenium atom of 3 has a tetragonal pyramidal coordination environment with a vacant coordination site sterically protected by the Me substituents of the ligands. Thus, compound 3 should be an attractive target for future coordination studies.

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Section: Spectroscopic Characterizationmentioning

confidence: 95%

Neutral and Cationic Hydridoruthenium Tetrakiscarbene Complexes

2010

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“…Abbreviations used to describe NMR data are as follows: bs, broad singlet; d, doublet; m, multiplet; q, quartet; s, singlet; sept, septet; t, triplet; vt, virtual triplet. The bis-phosphinite PONOP ligands 29 and Fe(PMe 3 ) 4 34 were prepared according to literature procedures.…”

Section: Methodsmentioning

confidence: 99%

“…29 They reported preparation of a trans -dihydride ruthenium complex with reactivity toward water and electrophiles. PONOP has since been coordinated to group 9 and 10 metals.…”

Section: Introductionmentioning

confidence: 99%

Synthesis and characterization of iron complexes based on bis-phosphinite PONOP and bis-phosphite PONOP pincer ligands

DeRieux

Wong

Schrodi

2014

Journal of Organometallic Chemistry

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A series of bis-phosphinite and bis-phosphite PONOP iron complexes were prepared and characterized by NMR and IR spectroscopy. Bis-phosphinite PONOP iron dichloride complexes (RPONOP)FeCl2 (RPONOP = 2,6-(R2PO)2(C5H3N) and R = iPr, tBu) were prepared through complexation of the free ligands with FeCl2 and their solid-state structures were determined. Bis-phosphite PONOP iron complexes (OEtPONOP)Fe(PMe3)2 and (CatPONOP)Fe(PMe3)2 (Cat = catechol) were synthesized through complexation of the free ligands to Fe(PMe3)4. Carbonyl complexes of both bis-phosphinite and bis-phosphite PONOP were prepared and characterized by IR. The monocarbonyl (iPrPONOP)Fe(CO)Cl2 was accessed through exposure of (iPrPONOP)FeCl2 to an atmosphere of CO and the CO stretching frequency was observed at 1969 cm−1. Dicarbonyl complexes (iPrPONOP)Fe(CO)2 and (OEtPONOP)Fe(CO)2 were accessed through reduction of the corresponding chloride complexes with sodium amalgam under a CO atmosphere. Carbonyl stretching frequencies for (iPrPONOP)Fe(CO)2 and (OEtPONOPFe)(CO)2 were observed at 1824 and 1876 cm−1, and at 1871 and 1927 cm−1 respectively. The bis-phosphite PONOP complexes exhibit a less electron rich metal center than the bis-phosphinite PONOP complexes, as would be expected based on the stronger π-acceptor character of these ligands. The electronic properties of the bis-phosphinite PONOP and bis-phosphite PONOP iron complexes are intermediate between previously reported PNP and PDI iron complexes, with the PONOP ligands exhibiting stronger electron donating ability than PDI ligands, but promoting a less electron rich metal center than found in analogous PNP iron complexes.

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“…Using the method for making the imine intermediate given in section 2.2, 500 mg (1.25 mmol) of PONOP [48]…”

Section: Immobilization Of Ponop On Bp-1mentioning

confidence: 99%

A methods study of immobilization of PONOP pincer transition metal complexes on silica polyamine composites (SPC)

Goni

Rosenberg

Meregude

et al. 2016

Journal of Organometallic Chemistry

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Immobilization of catalytically active transition metal complexes on silica polyamine composite (SPC) surfaces offers many advantages for applications in catalysis particularly for catalyst recovery and reuse. We report here the immobilization of PONOP pincer complexes of Ru, Rh, Ni and Pd on the poly(allylamine) SPC, BP-1 using the Mannich reaction. Three different methods have been investigated for synthesizing the PONOP pincer transition metal complexes on BP-1: 1) direct reaction of the preformed pincer complexes using a two step Mannich reaction; 2) immobilization of the PONOP ligand using the Mannich reaction followed by the addition of a transition metal compound of a given metal; 3) the stepwise construction of PONOP on BP-1 followed by addition of a transition metal compound. The immobilized complexes on BP-1 were characterized by FT-IR, solid-state CPMAS 13 C and 31 P NMR, as well as elemental analysis. Anchoring of the complexes on BP-1 was also evaluated by the metal loading data obtained from the digestion of the loaded composites followed by Atomic Absorption Spectroscopy (AAS) or Inductively Coupled Plasma Atomic Emission Spectroscopy

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Formation of Stabletrans-Dihydride Ruthenium(II) and 16-Electron Ruthenium(0) Complexes Based on Phosphinite PONOP Pincer Ligands. Reactivity toward Water and Electrophiles

Cited by 88 publications

References 62 publications

Neutral and Cationic Hydridoruthenium Tetrakiscarbene Complexes

Neutral and Cationic Hydridoruthenium Tetrakiscarbene Complexes

Synthesis and characterization of iron complexes based on bis-phosphinite PONOP and bis-phosphite PONOP pincer ligands

A methods study of immobilization of PONOP pincer transition metal complexes on silica polyamine composites (SPC)

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