Showing papers by "Malcolm L. H. Green published in 1979"
TL;DR: The lamellar compounds MPS3(M = Mn, Zn, Fe, or Ni) have been shown to react with neutral [Co(η-C5H5)2] and [Cr( Δ-C6H6)2], forming the intercalates of general stoicheiometry MPS 3[Co( Δ)-C5h5) 2]x and MPS4[Cr(δ-C 6H6]2]x.
Abstract: The lamellar compounds MPS3(M = Mn, Zn, Fe, or Ni) have been shown to react with neutral [Co(η-C5H5)2] and [Cr(η-C6H6)2] forming the intercalates of general stoicheiometry MPS3[Co(η-C5H5)2]x and MPS3[Cr(η-C6H6)2]x. The role of the solvent is quite important. Thus, MnPS3 intercalates [Cr(η-C6H6)2] together with benzene forming MnPS3[Cr(η-C6H6)2]0.24(C6H6)0.10. The compounds MnPS3 and ZnPS3 have also been shown to take up cationic species, giving the related intercalation products; this unexpected route to intercalation is briefly discussed.
40 citations
TL;DR: In this paper, it was shown that the mechanism of the reaction involves a reversible 1,2-hydrogen shift equilibrium between the intermediates [W(η-C5H5)2Me]- and [W[W(C5 H5]2Me]+.
Abstract: The reaction of [W(η-C5H5)2(C2H4)Me][PF6] with PMe2Ph gives [W(η-C5H5)2(CH2CH2PMe2Ph)Me][PF6](2) which eliminates ethylene when heated to give, in sequence, [W(η-C5H5)2(CH2PMe2Ph)H][PF6](3) and [W(η-C5H5)2Me(PMe2Ph)][PF6](4). Repeating this sequence with the deuteriated methyl analogues shows that the CD3 unit in (2) is reformed quantitatively in (4) and supports the proposal that the mechanism of the reaction involves a reversible 1,2-hydrogen shift equilibrium between the intermediates [W(η-C5H5)2Me]+ and [W(η-C5H5)2(CH2)H]+. The compounds [W(η-C5H5)2L(Me)](L = SEt2 or PPh3) and [W(η-C5H5)2Me(I)] have also been prepared and treated with PMe2Ph to give (3). Some implications of the 1,2-hydrogen shift (α elimination) are discussed.
31 citations
TL;DR: In this article, the mechanisms of photoinduced insertions of tungsten into aromatic and aliphatic C-H bonds are discussed, and the photoinduced reaction between [W(η-C5H5)2H2] and toluene, a to-luene-mesitylene mixture, and methyl propionate are also described.
Abstract: Photolysis of solutions of [W(η-C5H5)2H2] in fluorobenzene, o-xylene, anisole, p-chlorotoluene, p-xylene, mesitylene, p-methylanisole, and methyl benzoate gives the compounds [W(η-C5H5)2H(C6H4F-3 and -4)], [W(η-C5H5)2H(C6H3Me2-3,4)], [W(η-C5H5)2H(C6H4OMe-4)], [W(η-C5H5)2Cl(C6H4Me-4)], [W(η-C5H5)2(CH2C6H4Me-4)2], [W(η-C5H5)2(CH2C6H3Me2-3,5)2], [W(η-C5H5)2(CH2C6H4OMe-4)2], and [W(η-C5H5)2H(C6H4CO2Me-3 and -4)] together with [W(η-C5H5)2H(OCOPh)], respectively. Thermal decomposition of [W(η-C5H5)2H(Me)] in mesitylene gives [W(η-C5H5)2H(CH2C6H3Me2-3,5)]. Photolysis of this compound in p-xylene gives [W(η-C5H5)2(CH2C6H4Me-4)(CH2C6H3Me2-3,5)]. Photolysis of [W(η-C5H5)2H2] in tetra-methylsilane gives cis- and trans-[H(η-C5H5)W(σ: η5-C5H4)2W(η-C5H5)(CH2SiMe3)]. The photoinduced reaction between [W(η-C5H5)2H2] and toluene, a toluene–mesitylene mixture, and methyl propionate are also described. The mechanisms of these photoinduced insertions of tungsten into aromatic and aliphatic C–H bonds are discussed.
29 citations
TL;DR: In this paper, photolysis of an argon matrix at 10 K leads to a common product identified by i.U.r.v. spectroscopy as [(η-C5H5)2W] or (2)
Abstract: U.v. photolysis of [(η-C5H5)2WH2], [(η-C5H5)2WD2], [(η-C5H5)2WCO], or [(η-C5H5)2W(CH3)H] in an argon matrix at 10 K leads to a common product identified by i.r. spectroscopy as [(η-C5H5)2W], and similarly photolysis of [(η-C5H5)2MoH2] or [(η-C5H5)2MoCO] affords [(η-C5H5)2Mo]; trapping experiments with a CO matrix show that the elimination of H2 from [(η-C5H5)2-MH2](M = Mo or W) is close to concerted.
21 citations
TL;DR: Co-condensation of hafnium or zirconium atoms from an electron-gun furnace with arenes and trimethyl-phosphine gives good yields of the compounds [M(η-arene)2(PMe3)], M = Hf or Zr as discussed by the authors.
Abstract: Co-condensation of hafnium or zirconium atoms from an electron-gun furnace with arenes and trimethyl-phosphine gives good yields of the compounds [M(η-arene)2(PMe3)], M = Hf or Zr.
20 citations
TL;DR: The methylhydride [W(η-C5H5)2Me(H)] has been prepared by treatment of the compounds with Na[AlH2(OCH2CH2OMe)2] and PH(C6H4Me-4) with methyl iodide as mentioned in this paper.
Abstract: The methylhydride [W(η-C5H5)2Me(H)] has been prepared by treatment of the compounds [W(η-C5H5)2MeX], where X = I or OCOPh, with Na[AlH2(OCH2CH2OMe)2] Thermal decomposition of [W(η-C5H5)2Me(H)] in benzene, fluorobenzene, p-xylene, trimethyl phosphite, methanol, or dimethyl (4-tolyl)phosphine evolves methane and the compounds [W(η-C5H5)2R(H)], where R = Ph, C6H4F-3 or -4, CH2C6H4Me-4, OP(OMe)2, OMe, or PH(C6H4Me-4) are formed Treatment of [W(η-C5H5)2{PH(C6H4Me-4)}H] with methyl iodide gives [W(η-C5H5)2{PH (Me)(C6H4Me-4)}H]+ The oxidation of [W(η-C5H5)2Me2]+ which may be reduced to the parent dimethyl compound
20 citations
TL;DR: In this article, the precursors of the Co(η-etmcp) system have been described, such as tri-n-butyl(ethyltetramethylcyclopentadienyl)tin, Sn(etmctin)Bun3, and Co(nbutyl)Cl(µ-Cl)2Cl6.
Abstract: Tri-n-butyl(ethyltetramethylcyclopentadienyl)tin, Sn(etmcp)Bun3, reacts with cobalt(II) chloride to give, after treatment with chlorine, [{Co(etmcp)Cl(µ-Cl)}2] and [Co3(etmcp)2Cl6]. Using these compounds as precursors, many derivatives of the Co(η-etmcp) system have been prepared; examples are [(η-etmcp)Co(µ-Cl)3Co(η-etmcp)][FeCl4], [Co(η-etmcp)(PPh3)Cl2], [Co(η-etmcp)L2Cl][PF6][L2= Ph2P(CH2)2PPh2, or (PMe2Ph)2], [Co(η-etmcp)L3][PF6][L3=(NH3)3, (MeCN)3, (MeCN)2(Me2CNH), (CH2CHCN)3, η-benzene, or η-toluene], and [Co(η-etmcp)L2][L2=(η-C2H4)2, butadiene, or 1,5-C8H12].
16 citations
TL;DR: In this article, the compounds [Mo(η-C5H5)2R(CO)][PF6] and [W(W(C 5H5)-2(CH2CN)Cl] with PMe2Ph were described.
Abstract: The compounds [Mo(η-C5H5)2R(CO)][PF6](R = Me, σ-C3H5, CH2OMe, COMe, CH2CO2Me, or CH2CN) and [W(η-C5H5)2Me(CO)][PF6], have been prepared by addition of RX to [Mo(or W)(η-C5H5)2(CO)]. Similarly, the compounds [W(η-C5H5)2(C2H4)R″][PF6](R″=σ-C3H5, CH2CN, and CH2CO2Me) have been prepared by addition of R″X to [W(η-C5H5)2(C2H4)]. Treatment of [Mo(η-C5H5)2Me(CO)][PF6] with PMe2Ph gives [Mo(η-C5H5)2(COMe)(PMe2Ph)][PF6]. The compounds [W(η-C5H5)2(CH2CN)Cl]. [W(η-C5H5)2(CH2CN)(PMe2Ph)][PF6], [W(η-C5H5)2(η-MeC2Me)Me][PF6], [W(η-C5H5)2(O2CC6H4Br-o)Me], and [W(η-C5H5)2(O2CC6H4OH-o)Me] are also described.
14 citations
TL;DR: The trihydride [Mo(η-C5H5)(dppe)H3] reacts with butadiene giving the new compounds as discussed by the authors, which can be found in the literature.
Abstract: The new compounds [Mo(η-C5H5)2L2][PF6]2, [Mo(η-C5H5)(η3-C5H7)(dppe)], [Mo(η-C5H5)L2Cl3], [Mo(η-C5H5)(dppe)H3], [Mo(η-C5H5)(dppe) Br3]·C6H5Me, [Mo(η-C5H5)2(NCMe)2][PF6]2, [Mo(η-C5H5)2(dppm)H][PF6], [Mo(η-C5H5)(dppm)Cl][PF6]·0.5CH2Cl2, and [Mo(η-C5H5)(exo-H-C5H5)(dppm)][PF6]·CH2Cl2[L2= 1,2-bis (diphenylphosphino)ethane (dppe) or bis(diphenylphosphino)methane (dppm)] have been prepared. The trihydride [Mo(η-C5H5)(dppe)H3] reacts with butadiene giving [Mo(η-C5H5)(dppe)(η3-C3H4Me)].
13 citations
7 citations
TL;DR: In this paper, the new complexes [Co(η-C5H5)(η -2-MeC3H4)L][PF6] have been prepared and characterized.
Abstract: The new complexes [Co(η-C5H5)(η-2-MeC3H4)L][PF6](L = CO, PMe3, C5H5N, or NH3), [Co(η-C5H5)(η-1-MeC3H4)L′][PF6] and [Co(η-C5H5)(η-C3H5)L′][PF6](L′= CO or PMe3), [Co(η-C5H5)(η-2-MeC3H4)I], [Co(η-C5H5)(PMe3)(CO)], [Co(η-C5H5)(PMe3)3][PF6]2, [Co(η-C5H5)(PMe2Ph)I2], [Co(η-C5H5)(PMe2Ph)2H][PF6], and [Co(η-C5H5)(PMe3)Me2] have been prepared and characterized.
TL;DR: The rate of thermal rearrangement of the compounds [W(η-C5H5)2H(CH2PR3)]PF6 to PF6 increases in the order R3 = Ph2Me>PhMe2>Me3, and when R3= Me3 the two compounds are found to be in equilibrium in solution as mentioned in this paper.
Abstract: The rate of the thermal rearrangement of the compounds [W(η-C5H5)2H(CH2PR3)]PF6 to [W(η-C5H5)2Me(PR3)]PF6 increases in the order R3= Ph2Me>PhMe2>Me3, and when R3= Me3 the two compounds are found to be in equilibrium in solution; when R3= Ph2Me the PMePh2 group exchanges with added PMe3 giving [W(η-C5H5)2H(CH2PMe3)]PF6.
TL;DR: The syntheses of the new compounds {[(η-C5H5)MoR]2(μ-( η-c5H4-η -C5h4)-η −C5 h4)) and as discussed by the authors were described.
TL;DR: In this article, the precursors of the Co(η-etmcp) system have been described, such as tri-n-butyl(ethyltetramethylcyclopentadienyl)tin, Sn(etmctin)Bun3, and Co(nbutyl)Cl(µ-Cl)2Cl6.
Abstract: Tri-n-butyl(ethyltetramethylcyclopentadienyl)tin, Sn(etmcp)Bun3, reacts with cobalt(II) chloride to give, after treatment with chlorine, [{Co(etmcp)Cl(µ-Cl)}2] and [Co3(etmcp)2Cl6]. Using these compounds as precursors, many derivatives of the Co(η-etmcp) system have been prepared; examples are [(η-etmcp)Co(µ-Cl)3Co(η-etmcp)][FeCl4], [Co(η-etmcp)(PPh3)Cl2], [Co(η-etmcp)L2Cl][PF6][L2= Ph2P(CH2)2PPh2, or (PMe2Ph)2], [Co(η-etmcp)L3][PF6][L3=(NH3)3, (MeCN)3, (MeCN)2(Me2CNH), (CH2CHCN)3, η-benzene, or η-toluene], and [Co(η-etmcp)L2][L2=(η-C2H4)2, butadiene, or 1,5-C8H12].
TL;DR: In this article, 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.
TL;DR: In this article, the new complexes [Co(η-C5H5)(η -2-MeC3H4)L][PF6] have been prepared and characterized.
Abstract: The new complexes [Co(η-C5H5)(η-2-MeC3H4)L][PF6](L = CO, PMe3, C5H5N, or NH3), [Co(η-C5H5)(η-1-MeC3H4)L′][PF6] and [Co(η-C5H5)(η-C3H5)L′][PF6](L′= CO or PMe3), [Co(η-C5H5)(η-2-MeC3H4)I], [Co(η-C5H5)(PMe3)(CO)], [Co(η-C5H5)(PMe3)3][PF6]2, [Co(η-C5H5)(PMe2Ph)I2], [Co(η-C5H5)(PMe2Ph)2H][PF6], and [Co(η-C5H5)(PMe3)Me2] have been prepared and characterized.
TL;DR: In this article, the compounds [Mo(η-C5H5)2R(CO)][PF6] and [W(W(C 5H5)-2(CH2CN)Cl] with PMe2Ph were described.
Abstract: The compounds [Mo(η-C5H5)2R(CO)][PF6](R = Me, σ-C3H5, CH2OMe, COMe, CH2CO2Me, or CH2CN) and [W(η-C5H5)2Me(CO)][PF6], have been prepared by addition of RX to [Mo(or W)(η-C5H5)2(CO)]. Similarly, the compounds [W(η-C5H5)2(C2H4)R″][PF6](R″=σ-C3H5, CH2CN, and CH2CO2Me) have been prepared by addition of R″X to [W(η-C5H5)2(C2H4)]. Treatment of [Mo(η-C5H5)2Me(CO)][PF6] with PMe2Ph gives [Mo(η-C5H5)2(COMe)(PMe2Ph)][PF6]. The compounds [W(η-C5H5)2(CH2CN)Cl]. [W(η-C5H5)2(CH2CN)(PMe2Ph)][PF6], [W(η-C5H5)2(η-MeC2Me)Me][PF6], [W(η-C5H5)2(O2CC6H4Br-o)Me], and [W(η-C5H5)2(O2CC6H4OH-o)Me] are also described.