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Papers by John Harrod

Research paper thumbnail of The stereochemistry of Si—D addition to hydridocarbonyltris(triphenylphosphine)iridium(I)

Journal of Organometallic Chemistry, 1976

ABSTRACT

Research paper thumbnail of Book Reviews : The Reasonableness of Christianity

Research paper thumbnail of People before Buildings

Research paper thumbnail of ChemInform Abstract: Catalysis of Reactions of Si-H by Titanocene and Its Derivatives

ChemInform, 2000

ABSTRACT ChemInform is a weekly Abstracting Service, delivering concise information at a glance t... more ABSTRACT ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.

Research paper thumbnail of ChemInform Abstract: Hydrosilation (or Hydrosilylation?): A Personal Perspective on a Scientifically and Technologically Fascinating Chemical Methodology

Research paper thumbnail of Catalysis of reactions of SiH by titanocene and its derivatives

Coordination Chemistry Reviews, 2000

Research paper thumbnail of Photo-Redox Mechanism for the Reaction of �Cation-like� Zirconocene Silyl Complexes with Silanes

Organometallics, 2000

ABSTRACT A kinetic study of the photochemical reaction of [Cp2Zr(mu-SiH2Ph)](2)(2+)2[BBun(C6F5)(4... more ABSTRACT A kinetic study of the photochemical reaction of [Cp2Zr(mu-SiH2Ph)](2)(2+)2[BBun(C6F5)(4-n)](-) (1) with PhCH2SiH3 to give the analogous PhCH2SiH2 complex 2 was carried out using a combination of NMR and EPR spectroscopy to follow the rates of disappearance of reactants and the appearance of intermediates and products. The paramagnetic intermediate [Cp2ZrIII](+)[BBun(C6F5)(4-n)](-) (3) is produced with a quantum efficiency of 0.96 +/- 0.16 on irradiation of 1 with light having lambda < 450 nm. The rate law and analysis of intermediates supports a Zr(IV)/Zr(III) redox mechanism in which the rate-determining step is photodecomposition of 1 to generate 3 and silyl radicals by homolytic dissociation. In the presence of excess PhCH2SiH3 3 reacts rapidly to give products.

Research paper thumbnail of Chemistry of phenoxo complexes. VI. Reactions of phenoxocopper(I) complexes with carbon tetrachloride

Research paper thumbnail of Polymerization of group 14 hydrides by dehydrogenative coupling

Acs Symposium Series, 1988

... Auteur(s) / Author(s). HARROD JF (1) ; Affiliation(s) du ou des auteurs / Author(s) Affiliati... more ... Auteur(s) / Author(s). HARROD JF (1) ; Affiliation(s) du ou des auteurs / Author(s) Affiliation(s). (1) McGill univ., dep. ... Anglais Editeur / Publisher. Oxford University Press, Cary, NC, ETATS-UNIS (1974) (Revue) Mots-clés anglais / English Keywords. Mass spectrometry. ; ...

Research paper thumbnail of Catalytic Dehydro- and Dehydrosilyl-Coupling: New Routes to Inorganic and Hybrid Organic/Inorganic Polymers

Research paper thumbnail of Reactions of Silanes with Allylic Alcohols Catalyzed by Titanocene Derivatives : An Approach to Catalytic Cross Dehydrocoupling/Co-Intramolecular Hydr Osilation

Journal of Organometallic Chemistry, 1995

ABSTRACT

Research paper thumbnail of Preparation and Properties of Dichlorobis(1-octene)platinum(II)

Research paper thumbnail of Phenoxo complexes of copper(II)

Research paper thumbnail of Reaction of silanes with unsaturated olefinic compounds

Research paper thumbnail of Nature of the Species Present in the Zirconocene Dichloride-Butyllithium Reaction Mixture

Organometallics, 1997

The thermal decomposition of dibutylzirconocene (1) at room temperature affords paramagnetic buty... more The thermal decomposition of dibutylzirconocene (1) at room temperature affords paramagnetic butylzirconocene(III) (11), zirconocene(III) hydride (12), the diamagnetic butenylzirconocene(IV) hydride dimer 5a, and the 1,1-bis(cyclopentadienyl)-2-methyl-3-(zirconocenyl hydride)-1-zirconacyclobutane(IV) dimer 9. Initially, decomposition furnishes crotylzirconocene(IV) hydride (3a), followed by 1,1-bis(cyclopentadienyl)-2-ethyl-1-zirconacyclopropane(IV) (2a) and 1,1-bis(cyclopentadienyl)-3,4-diethyl-1-zirconacyclopentane(IV) (4a), listed in the order of appearance. This order suggests that the primary decomposition reaction is a γ-H abstraction, which leads to the formation of 1,1-bis(cyclopentadienyl)-2methyl-1-zirconacyclobutane(IV) (6a). The latter was not observed experimentally but is postulated on the basis of secondary products. Reactions leading to the above compounds are discussed from mechanistic and thermochemical points of view. The reported compounds have been characterized by either EPR or multidimensional, multinuclear NMR spectroscopy. Compound 3a has also been synthesized independently from zirconocene chloride hydride and crotylmagnesium bromide and undergoes the same rearrangements into 2a and then 4a. The allyl analog 3b, synthesized from zirconocene chloride hydride and allylmagnesium bromide, exhibits the same behavior and rearranges into 1,1-bis(cyclopentadienyl)-3,4dimethyl-1-zirconacyclopentane (4b).

Research paper thumbnail of Room temperature vulcanizing compositions

Research paper thumbnail of A review of: "Inorganic Reaction Mechanisms. Vol. 6.A Specialist Periodical Report (The Chemical Society, London, 1979) Senior Reporter: A. McAuley, University of Victoria, Canada. xix 472 pp., $75.00

Syn Reactiv Inorg Metal Org C, 1980

Research paper thumbnail of Polymerization of Phenols on Metallic Copper

Research paper thumbnail of A general synthesis of titanocene(III) complexes Cp 2TiX(PMe 3) (X=F, Cl, Br, I, Me, SMe) by comproportionation of Cp 2TiX 2 and Cp 2Ti(PMe 3)

Inorg Chem Commun, 1999

The titanocene(III) complexes Cp2TiX(PMe3) (X=F, Cl, Br, I, Me, SMe) are readily synthesized by c... more The titanocene(III) complexes Cp2TiX(PMe3) (X=F, Cl, Br, I, Me, SMe) are readily synthesized by comproportionation reactions of Cp2Ti(PMe3)2 and Cp2TiX2. The products are characterized by EPR spectroscopy.

Research paper thumbnail of Process for reaction of silanic hydrogen with unsaturated organic compounds

Research paper thumbnail of The stereochemistry of Si—D addition to hydridocarbonyltris(triphenylphosphine)iridium(I)

Journal of Organometallic Chemistry, 1976

ABSTRACT

Research paper thumbnail of Book Reviews : The Reasonableness of Christianity

Research paper thumbnail of People before Buildings

Research paper thumbnail of ChemInform Abstract: Catalysis of Reactions of Si-H by Titanocene and Its Derivatives

ChemInform, 2000

ABSTRACT ChemInform is a weekly Abstracting Service, delivering concise information at a glance t... more ABSTRACT ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.

Research paper thumbnail of ChemInform Abstract: Hydrosilation (or Hydrosilylation?): A Personal Perspective on a Scientifically and Technologically Fascinating Chemical Methodology

Research paper thumbnail of Catalysis of reactions of SiH by titanocene and its derivatives

Coordination Chemistry Reviews, 2000

Research paper thumbnail of Photo-Redox Mechanism for the Reaction of �Cation-like� Zirconocene Silyl Complexes with Silanes

Organometallics, 2000

ABSTRACT A kinetic study of the photochemical reaction of [Cp2Zr(mu-SiH2Ph)](2)(2+)2[BBun(C6F5)(4... more ABSTRACT A kinetic study of the photochemical reaction of [Cp2Zr(mu-SiH2Ph)](2)(2+)2[BBun(C6F5)(4-n)](-) (1) with PhCH2SiH3 to give the analogous PhCH2SiH2 complex 2 was carried out using a combination of NMR and EPR spectroscopy to follow the rates of disappearance of reactants and the appearance of intermediates and products. The paramagnetic intermediate [Cp2ZrIII](+)[BBun(C6F5)(4-n)](-) (3) is produced with a quantum efficiency of 0.96 +/- 0.16 on irradiation of 1 with light having lambda < 450 nm. The rate law and analysis of intermediates supports a Zr(IV)/Zr(III) redox mechanism in which the rate-determining step is photodecomposition of 1 to generate 3 and silyl radicals by homolytic dissociation. In the presence of excess PhCH2SiH3 3 reacts rapidly to give products.

Research paper thumbnail of Chemistry of phenoxo complexes. VI. Reactions of phenoxocopper(I) complexes with carbon tetrachloride

Research paper thumbnail of Polymerization of group 14 hydrides by dehydrogenative coupling

Acs Symposium Series, 1988

... Auteur(s) / Author(s). HARROD JF (1) ; Affiliation(s) du ou des auteurs / Author(s) Affiliati... more ... Auteur(s) / Author(s). HARROD JF (1) ; Affiliation(s) du ou des auteurs / Author(s) Affiliation(s). (1) McGill univ., dep. ... Anglais Editeur / Publisher. Oxford University Press, Cary, NC, ETATS-UNIS (1974) (Revue) Mots-clés anglais / English Keywords. Mass spectrometry. ; ...

Research paper thumbnail of Catalytic Dehydro- and Dehydrosilyl-Coupling: New Routes to Inorganic and Hybrid Organic/Inorganic Polymers

Research paper thumbnail of Reactions of Silanes with Allylic Alcohols Catalyzed by Titanocene Derivatives : An Approach to Catalytic Cross Dehydrocoupling/Co-Intramolecular Hydr Osilation

Journal of Organometallic Chemistry, 1995

ABSTRACT

Research paper thumbnail of Preparation and Properties of Dichlorobis(1-octene)platinum(II)

Research paper thumbnail of Phenoxo complexes of copper(II)

Research paper thumbnail of Reaction of silanes with unsaturated olefinic compounds

Research paper thumbnail of Nature of the Species Present in the Zirconocene Dichloride-Butyllithium Reaction Mixture

Organometallics, 1997

The thermal decomposition of dibutylzirconocene (1) at room temperature affords paramagnetic buty... more The thermal decomposition of dibutylzirconocene (1) at room temperature affords paramagnetic butylzirconocene(III) (11), zirconocene(III) hydride (12), the diamagnetic butenylzirconocene(IV) hydride dimer 5a, and the 1,1-bis(cyclopentadienyl)-2-methyl-3-(zirconocenyl hydride)-1-zirconacyclobutane(IV) dimer 9. Initially, decomposition furnishes crotylzirconocene(IV) hydride (3a), followed by 1,1-bis(cyclopentadienyl)-2-ethyl-1-zirconacyclopropane(IV) (2a) and 1,1-bis(cyclopentadienyl)-3,4-diethyl-1-zirconacyclopentane(IV) (4a), listed in the order of appearance. This order suggests that the primary decomposition reaction is a γ-H abstraction, which leads to the formation of 1,1-bis(cyclopentadienyl)-2methyl-1-zirconacyclobutane(IV) (6a). The latter was not observed experimentally but is postulated on the basis of secondary products. Reactions leading to the above compounds are discussed from mechanistic and thermochemical points of view. The reported compounds have been characterized by either EPR or multidimensional, multinuclear NMR spectroscopy. Compound 3a has also been synthesized independently from zirconocene chloride hydride and crotylmagnesium bromide and undergoes the same rearrangements into 2a and then 4a. The allyl analog 3b, synthesized from zirconocene chloride hydride and allylmagnesium bromide, exhibits the same behavior and rearranges into 1,1-bis(cyclopentadienyl)-3,4dimethyl-1-zirconacyclopentane (4b).

Research paper thumbnail of Room temperature vulcanizing compositions

Research paper thumbnail of A review of: "Inorganic Reaction Mechanisms. Vol. 6.A Specialist Periodical Report (The Chemical Society, London, 1979) Senior Reporter: A. McAuley, University of Victoria, Canada. xix 472 pp., $75.00

Syn Reactiv Inorg Metal Org C, 1980

Research paper thumbnail of Polymerization of Phenols on Metallic Copper

Research paper thumbnail of A general synthesis of titanocene(III) complexes Cp 2TiX(PMe 3) (X=F, Cl, Br, I, Me, SMe) by comproportionation of Cp 2TiX 2 and Cp 2Ti(PMe 3)

Inorg Chem Commun, 1999

The titanocene(III) complexes Cp2TiX(PMe3) (X=F, Cl, Br, I, Me, SMe) are readily synthesized by c... more The titanocene(III) complexes Cp2TiX(PMe3) (X=F, Cl, Br, I, Me, SMe) are readily synthesized by comproportionation reactions of Cp2Ti(PMe3)2 and Cp2TiX2. The products are characterized by EPR spectroscopy.

Research paper thumbnail of Process for reaction of silanic hydrogen with unsaturated organic compounds

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