135 results for 2000, Nicholson, Brian K., Journal article

  • New ruthenium carbonyl clusters containing unusual 5-sulfido-, 4-benzyne-, and thianthrene-derived ligands: Insertion of ruthenium into the thianthrene ring by C-S activation

    Hassan, Mohammad R.; Kabir, Shariff E.; Nicholson, Brian K.; Nordlander, Ebbe; Uddin, Md. Nazim (2007-07-01)

    Journal article
    University of Waikato

    Treatment of [Ru3(CO)12] with thianthrene in refluxing toluene afforded [( 4-S)Ru4( -CO)2(CO)9( 4- 2-C6H4)] (1), [( 5-S)Ru6( -CO)2(CO)15( - 3-C12H8S)] (2), and [( 5-S)Ru5( -CO)2(CO)11( - 3-C12H8S)( 4- 2-C6H4)] (3) in 18%, 8%, and 16% yields, respectively. Thermolysis of 2 in refluxing heptane gave compounds 1 and 3. A similar thermolysis of 3 in refluxing toluene gave 1 in 90% yield. Treatment of 3 with neat MeCN afforded the labile compound [( 5-S)Ru5( -CO)2(CO)10( - 3-C12H8S)( 4- 2-C6H4)(MeCN)] (4) in 73% yield. The reaction of 4 with P(OMe)3 gave the substitution product [( 5-S)Ru5( -CO)2(CO)10( - 3-C12H8S)( 4- 2-C6H4){P(OMe)3}] (5) in 52% yield. Compounds 1-4 have been structurally characterized. Compound 1 contains a 4-capping sulfido and a 4- 2-benzyne ligand, whereas 3, 4, and 5 contain 5-sulfido and 4- 2-benzyne ligands. The latter three compounds provide rare examples of 5-sulfido and metal-assisted opening of the thianthrene ligand on polynuclear centers. In compounds 1, 3, and 4 the 4- 2-benzyne ligand is perpendicular to the Ru4 face of the clusters and represents a previously uncharacterized bonding mode for benzyne.

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  • β-Cyclomanganated 1,5-diphenylpenta-1,4-dien-3-ones and their reactions with alkynes: routes to η5-pyranyl--- and η5-oxocycloheptadienyl---Mn(CO)3 complexes

    Tully, Warren; Main, Lyndsay; Nicholson, Brian K. (2001-08-01)

    Journal article
    University of Waikato

    1,5-Diphenylpenta-1,4-dien-3-ones (4) are cyclometalated with benzylpentacarbonylmanganese to form [[1-phenyl-2-((E)-3-phenylprop-2-en-1-oyl-κO)]ethenyl-κC1]tetracarbonylmanganese derivatives (5). Coupling of 5 with alkynes in some cases gives [4-phenyl-2-(2-phenylethenyl)pyranyl-η5]tricarbonylmanganese complexes (6) analogous to those previously reported for β-manganated chalcones, but in other cases an alternative cyclisation pathway subsequent to insertion of alkyne into the C---Mn bond leads to [6-oxo-4,7-diphenylcyclohepta-1,4-dienyl-1,2,3,4,5-η]tricarbonylmanganese complexes (7). The X-ray crystal structure determination is reported for one such compound, [6-oxo-2,4,7-triphenylcyclohepta-1,4-dienyl-1,2,3,4,5-η]tricarbonylmanganese (7a), derived from 1,5-diphenylpenta-1,4-dien-3-one and phenylacetylene. The 7-phenyl group is found to occupy the endo position, and a mechanism involving Mn-mediated aryl migration is suggested to explain this stereochemistry. The reaction of 7a with ammonium cerium(IV) nitrate gives a low yield of 2-nitro-3,5,7-triphenylcyclohepta-2,4,6-trien-1-one (9), whose structure was established by X-ray crystal structure analysis. The pyranyl complexes (6) provide the corresponding pyrylium triiodide salts (8) when demetalated with iodine.

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  • E/Z isomerism in monoalkylated derivatives of [Pt₂(μ-S)₂(PPh₃)₄] containing 2,4-dinitrophenylhydrazone substituents

    Ujam, Oguejiofo Theophilus; Devoy, Sarah M.; Henderson, William; Wilkins, Alistair L.; Nicholson, Brian K. (2011)

    Journal article
    University of Waikato

    Alkylation of [Pt₂(m-S)₂(PPh₃)₄] with 2,4-dinitrophenylhydrazone-functionalized alkylating agents XC6H4C{¼NNHC₆H₃(NO₂)₂}CH2Br (X¼H, Ph) gives monoalkylated cations [Pt₂(m-S){m-SCH₂C{¼NNHC₆H₃(NO₂)₂}C₆H₄X}(PPh₃)₄]⁺. An X-ray diffraction study on [Pt₂(m-S){m-SCH₂C{¼NNHC₆H₃(NO₂)₂}Ph}(PPh₃)₄]BPh₄ shows the crystal to be the Z isomer, with the phenyl ring and NHC₆H₃(NO₂)₂ groups mutually trans. ¹H- and ³¹P{¹H} NMR spectroscopic methods indicate a mixture of Z (major) and E (minor) isomers in solution, which slowly convert mainly to the E isomer. Reaction of [Pt₂(m-S)₂ (PPh₃)₄] with the dinitrophenylhydrazone of chloroacetone [ClCH₂C{¼NNH(C₆H₃(NO₂)₂}Me] and NaBPh₄ gives [Pt₂ (m-S){m-SCH₂C{¼NNHC₆H₃(NO₂)₂}Me}(PPh₃)₄]BPh₄, which exists as a single (E) isomer.

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  • Orthomercurated and cycloaurated derivatives of the iminophosphorane Ph3P NPh

    Brown, Samuel D.J.; Henderson, William; Kilpin, Kelly Joan; Nicholson, Brian K. (2007-03-01)

    Journal article
    University of Waikato

    Ortho-lithiation of Ph3P NPh followed by reaction with HgCl2 gave good yields of [Hg{C6H4(PPh2 NPh)-2}Cl], 3, which was characterised spectroscopically and by an X-ray crystal structure determination. This is an isomer of the product of direct mercuration of Ph3P NPh which occurs on the N-bonded phenyl ring [J. Vicente, J.A. Abad, R. Clemente, J. Lopez-Serrano, M.C. Ramirez de Arellano, P.G. Jones, D. Bautista, Organometallics, 22 (2003) 4248]. Transmetallation of 3 with [AuCl4]− gave the corresponding cycloaurated complex [Au{κ2-C,N-C6H4(PPh2 NPh)-2}Cl2], with a five-membered metallocyclic ring incorporating four different elements.

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  • The pterocellins: novel bioactive alkaloids from the marine Bryozoan Ptrerocella vesiculosa

    Yao, Biao; Prinsep, Michèle R.; Nicholson, Brian K.; Gordon, Dennis P. (2003-01-01)

    Journal article
    University of Waikato

    Two new alkaloids, pterocellins A and B, have been isolated from the New Zealand marine bryozoan Pterocella vesiculosa. Structural elucidation was achieved through NMR and mass spectral analysis in conjunction with a single-crystal X-ray diffraction study of pterocellin A. The pterocellins possess a novel heterocyclic skeleton and exhibit potent antitumor activity and antimicrobial activity in vitro but only modest activity in the in vivo hollow fiber assay at the National Cancer Institute.

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  • The composition of Ehrlich's salvarsan: Resolution of a century-old debate

    Lloyd, Nicholas C.; Morgan, Hugh W.; Nicholson, Brian K.; Ronimus, Ron S. (2004-08-01)

    Journal article
    University of Waikato

    Ehrlich introduced in 1910 the compound 3-amino-4-hydroxyphenylarsenic(I) [Salvarsan, arsphenamine, Ehrlich 606,] as a remedy for syphilis, a disease caused by the spirochaete bacterium Treponema pallidum. His methodical search for a specific curative for an identified disease can be regarded as the introduction of targeted chemotherapy.

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  • Coordination isomerism in salicylhydroxamate complexes of platinum(II) and palladium(II)

    Henderson, William; Evans, Cameron; Nicholson, Brian K.; Fawcett, John (2003-01-01)

    Journal article
    University of Waikato

    The syntheses of a range of platinum(II) and palladium(II) complexes containing salicylhydroxamate ligands are described. The ancillary ligands, together with the synthetic route, influence the coordination mode of the salicylhydroxamate ligand. Reaction of cis-[PtCl₂(PPh₃)₂] with salicylhydroxamic acid and trimethylamine in hot methanol gave O,O′-bonded [Pt{OC( NO)C₆H₄OH}(PPh₃)₂], but [PtCl₂(cod)](cod = cycloocta-1,5-diene) gave N,O-bonded [Pt{OC₆H₄C(O)NOH}(cod)]. Ligand substitution gives other N,O bonded complexes, including [Pt{OC₆H₄C(O)NOH}(PPh₃)₂]. Reaction of K₂PtCl₄ with 2 equiv. of EPh₃(E = As or Sb), salicylhydroxamic acid and excess trimethylamine gives products whose structures depend on E; AsPh₃ gives [Pt{OC( NO)C₆H₄OH}(AsPh₃)₂], while SbPh₃ gives [Pt{OC₆H₄C(O)NOH}(SbPh₃)₂].

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  • A low-toxicity method for the separation of lanosterol and dihydrolanosterol from commercial mixtures

    Kavtaradze, Levan K.; Manley-Harris, Merilyn; Nicholson, Brian K. (2004-09-01)

    Journal article
    University of Waikato

    We describe an inexpensive, low-toxicity and high-yielding method for the production of pure lanosterol and dihydrolanosterol from the commercially available mixture. Optimum conditions are presented for the one-pot production of the intermediate 24,25 vicinal diol of lanosterol acetate (via either epoxidation or hydroxyhalogenation) which is readily separated from the unreacted dihydrolanosterol acetate. The lanosterol diol can then be converted to pure (>97%) lanosterol. Hypophosphorous acid was used for both the conversion of the epoxide to the diol, and as a catalyst for the hydroxyhalogenation by N-halosuccinimides of the olefinic bond.

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  • Synthesis, characterisation, supramolecular aggregation and biological activity of phosphine gold(I) complexes with monoanionic thiourea ligands

    Henderson, William; Nicholson, Brian K.; Tiekink, Edward R. T. (2006-01-01)

    Journal article
    University of Waikato

    A series of phosphine gold(I) complexes containing monoanionic thiourea ligands has been synthesised by reaction of the appropriate precursor chloro complex, Ph₃PAuCl, Cy₃PAuCl, dppf(AuCl)₂ [dppf = Fe(η⁵-C₅H₄PPh₂)₂] or dppe(AuCl)₂ (dppe = Ph₂PCH₂CH₂PPh₂) with the thiourea and Me₃N base in methanol solution. The complexes have been fully characterised by elemental analysis, NMR spectrometry, electrospray mass spectrometry, and in several cases, by single-crystal X-ray diffraction studies. The crystallographic studies show that the ligands coordinate as a thiolate in each case with systematic variations in geometric parameters being readily ascribed to the influence of the N-bound substituents. In four of the structures, discernable supramolecular aggregation patterns are evident, leading to loosely associated dimers or chain motifs, the latter mediated by either Au S, N–H N or C–H O interactions. Cytotoxicity data, against the P388 leukemia cell line, and anti-microbial data are also reported.

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  • Dinuclear platinum(II) complexes containing ferrocenylalkyl–thiolate and –selenolate ligands

    Devoy, Sarah M.; Henderson, William; Nicholson, Brian K. (2013)

    Journal article
    University of Waikato

    Alkylation reactions of [Pt₂(μ-S)₂(PPh₃)₄] with haloalkylferrocenes FcCH₂Cl, Fc(CH₂)₆Br and Fc(CH₂)₁₁Br [Fc = (η⁵-C₅H₅)Fe(η⁵-C₅H₄)] gave the cationic μ-thiolate complexes [Pt₂(μ-S){μ-S(CH₂)nFc}(PPh₃)₄]⁺ (n = 1, 6, 11), isolated as PF₆⁻ and/or BPh₄⁻ salts, and characterised by ESI mass spectrometry, NMR spectroscopy, microelemental analysis, and by an X-ray structure determination on [Pt₂(μ-S){μ-SCH₂Fc}(PPh₃)₄]PF₆. The complex contains the typical folded {Pt₂(μ-S)₂} core with an axial ferrocenylmethylthiolate ligand. The corresponding selenolate complex [Pt₂ (μ-Se){μ-SeCH₂Fc}(PPh₃)₄]⁺ was similarly obtained by alkylation of [Pt₂(μ-Se)₂ (PPh₃)₄] with FcCH₂Cl, and isolated as PF₆⁻ and BPh₄⁻ salts. The attempted liberation of FcCH₂SH from [Pt₂(μ-S){μ-SCH₂Fc}(PPh₃)₄]+ using Na₂S was not successful.

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  • Dimeric rhodium(III), iridium(III) and ruthenium(II) thiosalicylate complexes

    Henderson, William; Nicholson, Brian K.; Oliver, Allen G.; Rickard, Clifton E.F. (2001-04-01)

    Journal article
    University of Waikato

    Reactions of the chloride-bridged dimers [LMCl(μ-Cl)]₂ (M=Rh, Ir; L=Cp*=η⁵-C₅Me₅; M=Ru, L=η⁶-p-cymene) with two mole equivalents of thiosalicylic acid (HSC₆H₄CO₂H, H₂tsal) and excess base gives the dimeric rhodium(III), iridium(III) and ruthenium(II) thiosalicylate complexes [LM(tsal)]₂. Reaction of the complex [Cp*RhCl₂(PPh₂)] with one equivalent of H₂tsal and triethylamine in dichloromethane gives a mixture of the dimer [Cp*Rh(tsal)]₂ and the phosphine complex [Cp*Rh(tsal)(PPh₃)]; upon recrystallisation, pure dimer is obtained. A single-crystal X-ray diffraction study on the rhodium and ruthenium dimers reveals the expected thiolate-bridged M₂(μ-S)₂ unit. Electrospray mass spectrometry (ESMS) is a useful technique in studying the chemistry of the thiosalicylate complexes, all complexes giving strong [M+H]⁺ ions. With added thiosalicylic acid, cations of the type [(LM)₂(Htsal)₃]⁺ were detected in the mass spectra.

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  • Thiourea monoanion and dianion complexes of rhodium(III) and ruthenium(II)

    Henderson, William; Nicholson, Brian K.; Dinger, Maarten B.; Bennett, Rachel L. (2002-10-01)

    Journal article
    University of Waikato

    The versatility of deprotonated thioureas as ligands is shown by the synthesis and characterisation of a range of rhodium(III) complexes of substituted thioureas, with support from a ruthenium(II) analogue in one case. Reaction of the complexes [LMCl(μ-Cl)]2 [M=Rh, L=η5-C5Me5 (Cp*); M=Ru, L=η6-p-cymene] with Na[MeNHC(S)NCN] and excess trimethylamine base gives the dinuclear complexes [LM{SC(=NCN)NMe}]2 containing chelate-bridging thiourea dianion ligands. The Ru complex was characterised by an X-ray diffraction study. The mononuclear complexes [Cp*Rh{SC(=NCN)NMe}(PPh3)] and [Cp*Rh{SC(=NPh)NPh}(PPh3)], containing chelating thiourea dianion ligands, were prepared by analogous reactions in the presence of triphenylphosphine. Reaction of [Cp*Rh{SC(=NCN)NMe}(PPh3)] with HCl, or [Cp*RhCl(μ-Cl)]2 with 2 equiv. of PPh3 and Na[MeNHC(S)NCN] (with no added base) gave the complex [Cp*RhCl{SC(=NCN)NHMe}(PPh3)], containing a (monodentate) S-bonded thiourea monoanion ligand, which was characterised by an X-ray diffraction study. The AsPh3 and SbPh3 analogues of this complex were also prepared and characterised. Reaction of [Cp*RhCl(μ-Cl)]2 with 2 equiv. of PPh3 or SbPh3 and PhNHC(S)NHPh or various trisubstituted thioureas PhNHC(S)NR1R2, triethylamine and NaBPh4 gave a range of cationic complexes [Cp*Rh{SC(=NR1R2)NPh}(EPh3)]+ (E=P, Sb), as their tetraphenylborate salts, in which the thiourea is bonded as a monoanion through the S and the NPh group. The corresponding reaction utilising 1,6-bis(diphenylphosphino)hexane (dpph) gave the dinuclear complex [Cp*Rh{SC(=N(CH2CH2)2O)NPh}]2(μ-η2-dpph) (BPh4)2.

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  • Synthesis and crystal structure of the first complex containing a chelating selenourea dianion ligand

    Nicholson, Brian K.; Henderson, William; Dinger, Maarten B. (2003-11-01)

    Journal article
    University of Waikato

    Reaction of N,N′-diphenylselenourea, PhNHC(Se)NHPh, with cis-[PtCl2(PPh3)2] and triethylamine in hot methanol gives the first example of a selenourea dianion complex, [Pt{SeC(=NPh)NPh}(PPh3)2] isolated as a yellow solid in high yield. The structure of the complex was determined by X-ray crystallography and found to be similar to the related thiourea dianion complex [Pt{SC(=NPh)NPh}(PPh3)2], with a Pt---Se---C---N four-membered ring. The antitumour activity (P388 murine leukaemia cells) of the selenourea dianion complex was determined, together with a small selection of related platinum(II)-thiourea dianion complexes (prepared by an analogous method) for comparison. The complex [Pt{SC(=NMe)NMe}(PPh3)2] showed high activity [IC50 1.0 μM], with the other complexes showing moderate to low activity.

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  • Platinum(II) complexes of chelating and monodentate thiourea monoanions incorporating chiral, fluorescent or chromophoric groups

    Henderson, William; Nicholson, Brian K.; Rickard, Clifton E.F. (2001-08-01)

    Journal article
    University of Waikato

    The reaction of cis-[PtCl2(PPh3)2] with trisubstituted thioureas [R1R2NC(=S)NHR3] in refluxing methanol with triethylamine base, followed by addition of NaBPh4 gives the salts [Pt{SC(=NR1R2)NR3}(PPh3)2]BPh4 in high yield; a range of thiourea substituents, including chiral, fluorescent and chromophoric groups can be incorporated. The azo dye-derived complex [Pt{SC(=N(CH2CH2)2O)NC6H4N=NC6H4NMe2}(PPh3)2]BPh4 has been characterised by a single-crystal X-ray diffraction study. The formation of a fluorescein-derivatised platinum-thiourea complex is also described. Reaction of cis-[PtCl2(PPh3)2] with PhNHC(S)NHPh or EtNHC(S)NHEt, triethylamine and NaBPh4 gives, respectively, [Pt{SC(=NHPh)NPh}(PPh3)2]+ and the known cation [Pt{SC(=NHEt)NEt}(PPh3)2]+, isolated as tetraphenylborate salts. Reaction of cis-[PtCl2(PPh3)2] with an excess of Na[MeNHC(S)NCN] in methanol gives the bis(thiourea monoanion) complex trans-[Pt{SC(=N---CN)NHMe}2(PPh3)2], characterised by NMR spectroscopy and an X-ray crystal structure determination. When cis-[PtCl2(PPh3)2] is reacted with 1 equiv. of Na[MeNHC(S)N---CN] in methanol, with added NaBPh4, a mixture of isomers of the [Pt{SC(=NHCN)NMe}(PPh3)2]+ cation is obtained.

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  • Synthesis and characterization of new trimetallic complexes with {Pt₂Au(μ-S) ₂} ⁿ⁺ (n=2, 3) cores containing C, N and N, N donor ligands

    White, Bradley C.; Henderson, William; Hor, T.S. Andy; Nicholson, Brian K. (2013)

    Journal article
    University of Waikato

    Reactions of the dinuclear platinum(II) sulfide complex [Pt ₂(μ-S) ₂(PPh ₃) ₄] with a range of gold(III) dichloride complexes [AuLCl ₂] containing C, N- or N, N-cycloaurated ligands L gives a new series of dicationic adducts [Pt ₂(μ-S) ₂(PPh ₃) ₄AuL] ²⁺, isolated as their PF ₆ - salts. The complexes investigated are [Au{C₆₋H ₄(CH ₂NMe ₂)-2}Cl ₂], [Au{C ₆H ₃(CH ₂NMe ₂)-2-(OMe)-5}Cl ₂], [Au{NC ₅H ₄(CH ₂C ₆H ₄)-2}Cl ₂], [Au{NC ₅H ₄(COC ₆H ₄)-2}Cl ₂] and [Au{NC ₅H ₄(CONH)-2}Cl ₂]. An X-ray structure determination on the picolinamide-derived complex [Pt ₂(μ-S) ₂(PPh ₃) ₄Au{NC ₅H ₄(CONH)-2}](PF₆) ₂ was not of sufficiently high quality for detailed discussion, but confirmed the atom connectivity. Reactions of [Pt ₂(μ-S) ₂(PPh ₃) ₄] with [AuCl ₂(bipy)]PF ₆ (L=bipy=2,2'-bipyridine) and [AuCl ₂(phen)]Cl (L=phen=1,10-phenanthroline) gives the corresponding tricationic adducts [Pt ₂(μ-S) ₂(PPh ₃) ₄AuL] ³⁺, also isolated as their PF ₆⁻ salts. The complexes are characterised by NMR spectroscopy, electrospray mass spectrometry and microelemental analyses. Biological assay data of a selection of these new complexes towards the P388 murine leukemia cell line, as well as a range of antimicrobial tests, reveals overall low activity compared to other cycloaurated gold(III) complexes.

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  • Influence of chain length on mono- versus di-alkylation in the reactivity of [Pt₂(μ-S)₂(PPh₃)₄] towards α,ω-dihalo-n-alkanes; a synthetic route to platinum(II) ω-haloalkylthiolate complexes

    Devoy, Sarah M.; Henderson, William; Nicholson, Brian K.; Hor, T.S. Andy (2010)

    Journal article
    University of Waikato

    The reactions of [Pt₂(μ-S)₂(PPh₃)₄] with a,x-dibromoalkanes Br(CH₂)nBr (n = 4, 5, 6, 8, 12) gave monoalkylated [Pt₂(μ-S){μ-S(CH₂)nBr}(PPh₃)₄]⁺ and/or di-alkylated [Pt₂(μ-S(CH₂)nS}(PPh₃)₄]²⁺ products, depending on the alkyl chain length and the reaction conditions. With longer chains (n = 8, 12), intramolecular di-alkylation does not proceed in refluxing methanol, with the mono-alkylated products [Pt₂ (μ-S){μ-S(CH₂)nBr}(PPh₃)₄]⁺ being the dominant products when excess alkylating agent is used. The bridged complex [{Pt₂(μ-S)₂(PPh₃)₄}₂{μ-(CH₂)12}]²⁺ was accessible from the reaction of [Pt₂ (μ-S)₂(PPh₃)₄] with 0.5 mol equivalents of Br(CH₂)12Br. [Pt₂(μ-S){μ-S(CH₂)₄Br}(PPh₃)₄]⁺ can be cleanly isolated as its BPh₄⁻ salt, but undergoes facile intramolecular di-alkylation at -18 degree C, giving the known species [Pt₂(μ-S(CH₂)₄S}(PPh₃)₄]²⁺. The reaction of I(CH₂)₆I with [Pt₂(μ-S)₂(PPh₃)₄] similarly gives [Pt₂ (μ-S){μ-S(CH₂)₆I}(PPh₃)₄]⁺, which is fairly stable towards intramolecular di-alkylation once isolated. These reactions provide a facile route to x-haloalkylthiolate complexes which are poorly defined in the literature. X-ray crystal structures of [Pt₂(μ-S){μ-S(CH₂)₅Br}(PPh₃)₄]BPh₄ and [Pt₂(μ-S(CH₂)₅S} (PPh₃)₄](BPh₄)₂ are reported, together with a study of these complexes by electrospray ionisation mass spectrometry. All complexes fragment by dissociation of PPh₃ ligands, and the bromoalkylthiolate complexes show additional fragment ions [Pt₂(μ-S){μ-S(CH₂)n_2CH=CH₂}(PPh₃)m]⁺ (m = 2 or 3; m – 4), most significant for n = 4, formed by elimination of HBr.

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  • Synthesis and characterisation of four- and eight-membered ring auralactam complexes

    Henderson, William; Nicholson, Brian K.; Oliver, Allen G. (2001-02-01)

    Journal article
    University of Waikato

    The reactions of the cyclo-aurated gold(III) dihalide complex [{C6H3 (CH2NMe2)-2-(OMe)-5}AuCl2] with N-cyanoacetylurethane [NCCH2C(O)NHCO2Et], 2-benzoylacetanilide [PhC(O)CH2C(O)NHPh] and acetoacetanilide [MeC(O)CH2C(O)NHPh], and [{C6H4 (CH2NMe2)-2}AuCl2] with acetoacetanilide in dichloromethane with excess silver(I) oxide gives the first examples of auralactam complexes, containing Au-NR-C(O)-CHR′ four-membered rings. A single-crystal X-ray diffraction study on the complex [{C6H4 (CH2NMe2)-2}Au{NPhC(O)CH(COMe)}] reveals similar structural features to related metallalactam complexes of platinum(II) and palladium(II). When a CDCl3 solution of the complex [{C6H3 (CH2NMe2)-2-(OMe)-5}Au{N(CO2Et)C(O)CHCN}] is allowed to stand for 18 h, a novel dimerisation reaction occurs, giving the insoluble product [{C6H3 (CH2NMe2)-2-(OMe) 5}Au{N(CO2Et)C(O)CHCN}]2 2CDCl3, characterised by an X-ray structure determination. The dimer contains an eight-membered Au-N-C(O)-C-Au-N-C(O)-C ring.

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  • Camphene-derived primary and hydroxymethyl phosphines

    Berrigan, Rebecca A.; Russell, Douglas K.; Henderson, William; Leach, Meto T.; Nicholson, Brian K.; Woodward, Gary; Harris, Christopher (2001-01-01)

    Journal article
    University of Waikato

    Thermal disproportionation of (2,2-dimethylbicyclo[2.2.1]hept-3-ylmethyl)phosphinic acid (endo-8-camphanylphosphinic acid, camPO₂H₂) yields the primary phosphine (2,2-dimethylbicyclo[2.2.1]hept-3-ylmethyl)phosphine (camPH₂). The compound has been characterised by NMR spectroscopy, and as its tris(hydroxymethyl)phosphonium chloride salt [camP(CH₂OH)₃]Cl, synthesised by reaction with excess formaldehyde and hydrochloric acid. The X-ray crystal structure of this phosphonium salt is reported, confirming the endo position of the phosphonium group. On treatment with triethylamine base, camP(CH₂OH)₃ ⁺Cl⁻ is converted to the hydroxymethylphosphine camP(CH₂OH)₂. The sulfide and selenide of this phosphine have been prepared, together with the platinum(II) complex cis-[PtCl₂{camP(CH₂OH)₂}₂]. The gas-phase decomposition of camPH₂ has been investigated using the technique of IR laser powered homogeneous pyrolysis. Results indicate the initial elimination of phosphine, followed by the rearrangement and decomposition of camphene through two distinct pathways.

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  • Substituted phenylarsonic acids; structures and spectroscopy

    Lloyd, Nicholas C.; Morgan, Hugh W.; Ronimus, Ron S.; Nicholson, Brian K. (2008)

    Journal article
    University of Waikato

    Full NMR and ESI-MS spectra, and differential scanning calorimeter data are presented for 15 substituted phenylarsonic acids, including two new fluoro-substituted examples. X-ray crystal structure determinations of five examples (phenylarsonic acid and the 4-fluoro-, 4-fluoro-3-nitro-, 3-amino-4-hydroxy- and 3-amino-4-methoxy-substituted derivatives) were determined and the H-bonding crystal-packing patterns analysed.

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  • Bis[μ-bis(diphenylphosphino)methane-К²P:P’]bis[(saccharinato-КN)- palladium(I)] dichloromethane solvate

    Henderson, William; Nicholson, Brian K.; Chung, Dong C. (2002)

    Journal article
    University of Waikato

    The dimeric palladium(I) saccharinate complex [Pd₂(sac)₂(dppm)₂], has been characterized as its di¬chloro¬methane solvate, i.e. [Pd₂(C₇H₄NO₃S)₂(C₂₅H₂₂P₂)₂]•CH₂Cl₂. The complex features a Pd—Pd bond bridged by two dppm ligands, with the saccharinate ligands N-bonded trans to the Pd—Pd bond.

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