A. B. Goel

Evidence for single electron transfer in the reduction of alcoholswith lithium aluminum hydride

Abstract EPR evidence supporting a single electron transfer mechanism in the reduction of secondary and tertiary alcohols to hydrocarbons with LiAlH 4 is presented.

Evidence supporting a single electron transfer pathway in the reduction of aromatic ketones by metal alkoxides. Lithium isopropoxide, an excellent reducing agent for aromatic ketones.

Abstract Reactions of various metal alkoxides with aromatic ketones have been shown to produce radical intermediate. Lithium isopropoxide has been found to be an excellent reducing agent for aromatic ketones and reduces benzophenone at a faster rate than does aluminum isopropoxide.

EPR evidence for a single electron transfer mechanism in reactions of aromatic ketones with lithium amides

Abstract Direct spectroscopic evidence (EPR) supporting a single electron transfer mechanism in the reaction of lithium amides with aromatic ketones is presented.

Reaction of magnesium hydride with pyridine: Formation of H3Mg2NC5H6, HMgNC5H6 and Mg(NC5H6)2

Abstract The reaction of magnesium hydride with excess pyridine at room temperature results in the formation of soluble bis( N -dihydropyridyl)magnesium which is shown by NMR spectra, to contain 1,2- and 1,4-dihydropyridine groups bound to magnesium. A similar reaction carried out at 60° C has been shown to form bis( N -diihydropyridyl)magnesium containing only 1,4-dihydropyridine groups. Formation of H 3 Mg 2 (NC 5 H 6 ) and HMg(NC 5 H 6 ) are also reported in the controlled reactions of pyridine with magnesium hydride.

Electron transfer in the reduction of primary halides by metal hydrides

Abstract The reactions of various main-group metal hydrides with 1-halo-5-hexenes and with 1-halo-2,2-dlmethyl-5-hexenes produce both straight chain and cyclized reduction products. The formation of cyclic hydrocarbons clearly indicates the presence of radical intermediates during the course of these reactions.

Formation of benzoic acid in the palladium(II) catalyzed cleavage of phenyl-antimony and phenyl-phosphorus groups of Ph3Sb and Ph3P

Abstract Palladium (II) catalyzed cleavage of phenyl-antimony and phenyl-phosphorus groups of Ph 3 Sb and Ph 3 P under carbon-dioxide or CO/NO atmosphere leading to benzoic acid, has been demonstrated.

Cyclopentadienylmagnesium Hydride. A convenient synthesis and study of reactions with organic substrates via single electron transfer.

Abstract Cyclopentadienylmagnesium hydride (CpMgH) has been prepared conveniently by the reaction of magnesium hydride with cyclopentadiene in THF. The compound is soluble in THF and is a dimer in this solvent. Evidence is presented that supports the single electron transfer nature of the reactions of CpMgH with selected aromatic ketones, trityl halides and polynuclear hydro-carbons. Visible and EPR spectral studies of the colored, paramagnetic intermediates are described.

Spectroscopic evidence for the reduction of alkyl halides by metal hydrides via a single electron transfer mechanism

Abstract This report provides spectroscopic evidence to support a single electron transfer pathway to describe the reaction of metal hydrides with alkyl halides by direct EPR observation of the radical formed in the reaction.

Preparation and 31P NMR studies of cationic methyl platinum(II) complexes containing mixed ligands

Abstract The preparation of some new cationic methylplatinum(II) complexes containing mixed ligands of general formula, [PtMe( LL )(L′)]+PF−6 1 [ LL =Ph2PC2H4PPh2 and L′ = Ph2MeP, Ph3As and (p-YC6H4)3P; Y = F, H, CH3, CH3O, (CH3)2N] and [PtMe( LL′ (L″)]+PF−6, 2 [ LL′ =Ph2PC2H4AsPh2 and L″ = (PhO)3P and (p-YC6H4)3P; Y = F, CH3, CH3O] has been described. The 31P NMR spectra of complexes 1 and 2 consisting of 36 and 12 lines respectively are discussed. the trans-effect of the para-substituted phosphines has been related to their electronic parameters by measuring the platinumphosphorous coupling constants (JPt-P) which follows the trend F

Synthesis and NMR Spectral Studies of Mixed Phosphine Platinum(II) Complexes

Abstract Mixed phosphine platinum (II) complexes of the type trans-PtC1 (P-C)L [where (P-C) = But 2 PCMe2CH2 and L = (p-YC6H4)3 P; Y = Cl, F, H, CH3, CH3O and (CH3)2N] have been synthesized by the bridge-splitting reactions of chloro-bridged dinuclear platinum(II) complex, [PtCl(P-C)]2, with para-substituted triphenyl phosphines. On the basis of the 12 line 31P NMR spectra which show large phosphorus-phosphorus coupling constants (JP-P′ ≈ 420 Hz), trans-configuration has been assigned. The trans-effect of the para-substituted phosphines has been related to their electronic parameters by measuring the platinum-phosphorus coupling constants (JPt-P) which follows the trend Cl < F < H < CH3 < CH3O < (CH3)2N.