Synthesis and Oxidation of Ruthenium Allyl Thioether Complexes Bearing Phosphite and Phosphonite Coligands [1]

Abstract

Ruthenium Complexes, Thioether, Sulfoxide, Epoxide, Dimethyldioxirane Halfsandwich ruthenium thiolate complexes bearing electron-withdrawing phosphite or phos phonite ligands were prepared from [CpRu(PPh3)2(SR)l (R = Ph, CH2Ph, Me) and triphenylphosphite or (5,5')-bis(binaphthylphosphonito)ethane (bbpe), respectively. Reaction with l-bromo-3-methyl-2-butene in the presence of NH4PF6 gave the corresponding allylthioether complexes [CpRu(PR'3)2(S(R)CH2CH=CMe2)]PF6. Treatment with an excess of dimethyl dioxirane (DMD) transformed the triphenylphosphite derivatives into diastereomeric (oxiranylmethyl)sulfoxide complexes with 18 -80% de. NMR monitoring of the reaction revealed that the oxidant attacks the sulfur atom and the C=C double bond with comparable rates. Sim ilar oxidation of the bbpe complexes gave mixtures of four diastereoisomers with ratios of (64 : 15 : 1 3 :8 ) and (51 : 24 : 15 : 10), respectively.

Vinylogue Mono‐ and Bimetallic Cationic Sesquifulvalene and Monohydro Sesquifulvalene Complexes for Second Harmonic Generation

“…The situation changes for the monohydro sesquifulvalene complexes, which reveal one electronic absorption band with λ max considerably smaller than λ(SHG) and a cut off at about 500 nm. (7), [25] formyl ruthenocene, [6] triphenylcarbenium hexafluorophosphate/tetrafluoroborate, [26] (tricarbonyl)(trispropionitrile)chromium(0), [27] (trisacetonitrile)(η 5 -cyclopentadienyl)-ruthenium() hexafluorophosphate, [28] (trisacetonitrile)(η 5 -pentamethylcyclopentadienyl)ruthenium() hexafluorophosphate, [29] (cylohepta-1,3,5-trienyl-1-methyl)diethylphosphonate [1d] were synthesised according to literature procedures.…”

Half-sandwich ruthenium complexes of pentafluorobenzenethiolato ligands

“…Cyclopentadienyl ruthenium thiolate complexes containing phosphine ligands are known in the literature [8][9][10][11][12][13][14][15]. They have been made by metathesis reactions of the corresponding chlorides with a variety of thiolate donors [8][9][10][11].…”

Crystal structure of bis[(R,R)-1,2-(binaphthylphosphonito)ethane]dichloridoiron(II) dichloromethane disolvate

“…The ligand was synthesized according to a literature procedure using (R)-BINOL (Steinmetz et al, 1999). The iron complex was synthesized as follows: in a nitrogen-filled glovebox, FeCl 2 Á1.5THF (6.0 mg, 0.030 mmol, 1 equivalent) was combined with (R,R)-BPE (50 mg, 0.08 mmol, 3 equivalents) in 10 ml THF and stirred in a 20 ml dram vial for 24 h. The THF was vacuumed off to yield a brown powder: 31 P{ 1 H} NMR (202 MHz, C 6 D 6 ): 257.72 ppm, singlet.…”