Showing papers by "Malcolm L. H. Green published in 1978"
TL;DR: In this paper, three simple rules are proposed that enable the prediction of the most favorable position of nucleophilic attack on 18 electron organotransition metal cations containing unsaturated hydrocarbon ligands.
251 citations
TL;DR: In this paper, a Ziegler-Natta-based mechanism for the stereospecific polymerization of olefins was proposed, which differs significantly from previous mechanisms in the proposal that it proceeds via a 1,2-hydrogen shift from the α-carbon of the polymer chain and formation of metallocycle and carbene intermediates.
Abstract: A mechanism for the stereospecific polymerization of olefins by Ziegler–Natta catalysts is developed which differs significantly from previous mechanisms in the proposal that it proceeds via a 1,2-hydrogen shift from the α-carbon of the polymer chain and formation of metallocycle and carbene intermediates.
129 citations
TL;DR: In this paper, the lattice expansions of the host disulfides on intercalation have been determined by powder x-ray diffraction and are discussed in relation to the orientation of the organometallic cation between the layers.
Abstract: Substituted cobaltocenes (RC/sub 5/H/sub 4/)/sub 2/Co(R = Me, i-Pr, and n-Bu) have been intercalated into the layered dichalcogenides TaS/sub 2/ and ZrS/sub 2/ by direct reaction of toluene solutions of the organometallic compounds and the solid disulfides. Intercalates of TaS/sub 2/ have also been prepared by ion exchange of the hydrated sodium intercalate with organometallic cations in aqueous solution. Lattice expansions of the host disulfides on intercalation have been determined by powder x-ray diffraction and are discussed in relation to the orientation of the organometallic cation between the layers. Some chemical reactions of the intercalates and some ion-exchange experiments in nonaqueous solvents are described.
57 citations
TL;DR: Co-condensation of niobium atoms from an electron gun furnace with benzene, toluene, or mesitylene gives good yields of the crystalline paramagnetic sandwich compounds [Nb(η-arene)2].
Abstract: Co-condensation of niobium atoms from an electron gun furnace with benzene, toluene, or mesitylene gives good yields of the crystalline paramagnetic sandwich compounds [Nb(η-arene)2].
21 citations
TL;DR: Co-condensation of tungsten atoms from an electron gun source with benzene, toluene, or mesitylene yields bis-(arene)tungsten compounds [(η-C6H3R3)2W] which are reversibly protonated by dilute acids to give the cations as discussed by the authors.
Abstract: Co-condensation of tungsten atoms from an electron gun source with benzene, toluene, or mesitylene yields bis-(arene)tungsten compounds [(η-C6H3R3)2W](R = H and/or Me) which are reversibly protonated by dilute acids to give the cations [(η-C6H3R3)2WH]+(R = H and/or Me).
18 citations
TL;DR: In this paper, the compounds [{(η-C5H5)(µ-{η1:η5-C 5H4})Mo}2] and [{ (η -C5 H5)X2] have been prepared, and the systems [M( √ C 5H5) X2 ], [M = Mo or W, X 2 = Cl2 or O] were presented.
Abstract: The compounds [{(η-C5H5)(µ-{η1:η5-C5H4})Mo}2] and [{(η-C5H5)(µ-[η1:η5-C5H4])WH}2] have been prepared; the systems [M(η-C5H5)X2](M = Mo or W, X2= Cl2 or O)–NaHg deoxygenate epoxides catalytically.
14 citations
TL;DR: In this paper, the compound [Mo(η-C5H5)2H{MgBr(thf)2}] is described, which reacts with CO2, PhCH2Br, C3H5Br, MeI, and MeCOCl to give a compound that can be expressed as follows:
Abstract: The compound [Mo(η-C5H5)2H{MgBr(thf)2}] is described. It reacts with CO2, PhCH2Br, C3H5Br, MeI, and MeCOCl to give [Mo(η-C5H5)2(CO)], [Mo(η-C5H5)2(CH2Ph)2], [Mo(η-C3H5)(η-C5H5)2][PF6], [Mo(η-C5H5)2HI], Mo(η-C5H5)2(COMe)H], and [Mo(η-C5H5)2(COMe)2] respectively. Reaction paths for these products are discussed.
13 citations
TL;DR: In this article, the trihydride [Ta(ν-C5H5)2H3] was formed in 42% yield from TaX5 with benzyl chloride and NaAlH2 (OCH2CH2OCH3)2.
8 citations
5 citations
TL;DR: In this article, the compounds [{(η-C5H5)(µ-{η1:η5-C 5H4})Mo}2] and [{ (η -C5 H5)X2] have been prepared, and the systems [M( √ C 5H5) X2 ], [M = Mo or W, X 2 = Cl2 or O] were presented.
Abstract: The compounds [{(η-C5H5)(µ-{η1:η5-C5H4})Mo}2] and [{(η-C5H5)(µ-[η1:η5-C5H4])WH}2] have been prepared; the systems [M(η-C5H5)X2](M = Mo or W, X2= Cl2 or O)–NaHg deoxygenate epoxides catalytically.
2 citations
01 Jan 1978
TL;DR: In this paper, the photolysis of {(η-C 5 H 5 )MoH} and {( η 1 :η 5 -C 5H 4 )} in benzene leads to a compound of stoichiometry C 20 H 18 Mo 2.
TL;DR: In this paper, the effects of removal of chloride in [Mo(η-C5H5)(dppe)2][PF6] gave rise to a mixture of isomers.
Abstract: Displacement of chloride in [Mo(η-C5H5)(η-C6H6)Cl] gives [Mo(η-C5H5)(η-C6H6)L][PF6], [L = PPh3, PMe2Ph, CO, C2H4, C2H2, or C2(CO2Me)2] or [Mo(η-C5H5)(η-C6H6)X](X = H or Me). Loss of benzene gives rise to [Mo(η-C5H5)(dppe)2][PF6], [Mo(η-C5H5)Cl(O)2], [Mo(η-C5H5)Cl2O], and [Mo(η-C5H5)(η-C8H8)][PF6]. Replacement of dppe in [Mo(η-C5H5)(dppe)2][PF6](or [BF4]) leads to the salts [Mo(η-C5H5)(dppe)L2][PF6], [L2=(CO)(NCMe), (CO)2, η4-C6H8, C4H6, C2Me2· or C2Ph2]. Oxidation of [Mo(η-C5H5)(dppe)2][BF4] by iodine gives paramagnetic [Mo(η-C5H5)(dppe)2][PF6]2. The compound [Mo(η-C5H5)(η-C8H8)][PF6] reacts with L = CO or PPh3 giving [Mo(η-C5H5)(η-C8H8)L][PF6] and with Ph2P[CH2]2PPh2(dppe) giving [Mo(η-C5H5)(η4-C8H8)-(dppe)][PF6]. The compound [Mo(η-C5H5)(η4-C4H6)(dppe)][PF6] exists in solutions as a mixture of isomers. These react with Na[Al H2(OCH2CH2OMe)2] giving a separable mixture of the η3-3-methylally compounds [Mo-(η-C5H5)(η3-MeCHCHCH2)(dppe)] where the allyllc group is oriented ‘up’ or ‘down’ relative to the η-C5H5 ring.