The photoreaction of pentacarbonyliron with 1,3-diene/monoolefin mixtures results in C-C coupling of the two organic substrates, forming a six-carbon chain which is coordinated to the Fe (CO) 3 moiety in a 1-a,4-6-n3 fashion. Using various 1,3- dienes and monoolefins carrying methyl and carboalkoxy substituents, the wide applicability of this process is demonstrated.

This thesis describes the determination of the crystal structures of one organo-metallic and three organic compounds. Originally the research programme had envisaged working on substances which were obtained by the corrosive action of hydrocarbon oils on metallic lead, but after some considerable time had been spent on attempting to crystallise these rather intractable materials, the research was switched to deal with other compounds of industrial importance which were more readily available in the Polytechnic. Of the four crystalline compounds investigated, two were connected with the inhibition of the corrosion of steel, one was an additive used in the polymer industry, and one was a molecular complex which had exhibited some unusual physico-chemical properties. X-ray intensity data were collected in several different ways. One crystal structure was solved from visually estimated photographic data, two sets of data were collected on our. Stoe Stadi-2 diffractometer which uses Weissenberg geometry, and one set which comprised over 7000 intensities, the largest data-set ever worked on in this Department, was recorded on the CAD-4 diffractometer at Queen Mary College, University of London, by arrangement with Dr M Hursthouse. A variety of techniques were used in working out the crystal structures. One was solved by the MULTAN direct methods computer program, two by the use of the NRC direct methods program using 12 relationships, and one by "trial-and-error" because none of the other methods produced any meaningful results. Refinement of all four structures was carried out using the NRC suite of programs implemented on our Polytechnic computers (DEC-IO, DEC-20, and VAX 11/750). Anisotropic thermal vibrations were allowed for, and hydrogen atom positions were calculated resulting in the conventional R-factors of 6.7, 6.1, 6.6 and 6.1% for the four structures. No abnormalities were encountered in the results for three of the structures, but the picric acid - naphthalene complex turned out to be disordered with some of.the picric acid molecules occupying an alternative orientation in the unit cell which resulted in displacement of the naphthalene molecules also, and the possibility of proton transfer within the picric acid molecule which was confirmed by differences in bond lengths and anisotropic temperature parameters.

M(cup)n complexes have been prepared (M = Cu, Ni, Fe, Co, Mn, or Zn ; n=2, M-=Fe ; n=3 cupH = cupferron) and structures have been proposed on the basis of spectroscopic, thermal and magnetic techniques. Their behaviour towards the Lewis bases pyridine, triphenyl- phosphine and hydroxylamine has been investigated. All of the M(cup)2 complexes, except when M = Zn or Fe, affords adducts on reaction with pyridine, whereas the complex Fe(cup)3 underwent an internal redox reaction. Internal redox behaviour was also observed when the complexes Cu(cup)2 and Fe(cup)3 were treated with triphenylphosphine. On the basis of the nature of the products arising from these reactions and from a kinetic study of the reaction of Cu(cup) with the phosphine, mechanistic proposals have been made.

The chemistry of 1,2-quinone monooximes hi« been reviewed. The synthesis of 5-amlno, 5-alkylamino and 5-acylamino substituted 1,2-benzoquinone monooximes was systematically studied. Thus, It has been found that 5-amino-1,2-benzoquinone-2-oxime (5-AqoH), 5-ethylamino-4-methyl 1-1,2- benzoquinone-2-ox I me (5-Et-4-MeqoH), 5-hexylamino-1,2-benzoquinone-2-oxime (5-HxqoH) and 5-heptylamino-1,2-benzoquinone-2-oxime (5-HptqoH) were best prepared by the reaction of the corresponding phenol with sodium nitrite In the presence of concentrated hydrochloric acid. Under these conditions, N-nitrosation was inhibited and the 1,2-benzoquinone- 2-oxlme hydrochlorides were formed. The 5-acylaminc1,2-benzoqulnone-2- oximes, 5-propionylamino-1,2-benzoquinone-2-oxime (5-PrqoH), 5-butyrylamino-l,2-benzoquinone-2-oxime (5-BuqoH), 5-pentanoylamino-1,2-benzoquinone-2-oxime (5-PeqoH), and 5—heptanoylamino-1,2-benzoquinone-2-oxime (5-HpqoH) were obtained from their metal complexes, since the direct reaction of the phenol with sodium nitrite failed to give the compounds giving the corresponding l,4-benzoquinone-4-oximes,3- proplonylamino-1,4-benzoquinone-4-oxime (3-PrqoH), 3-butyrylamino-1,4- benzoquinone-4-oxlme (3-BuqoH), 3-pentanoylamino-1,4-benzoquinone-4- oxime (3-PeqoH) and 3-heptanoylamino-1,4-benzoquinone-4-oxime (3-HpqoH) instead. Spectroscopic analysis has shown the compounds to exist in the quinone oximic rather than In the nitrosophenollc form. X-ray crystallographic studies of 5-HxqoH, 5-Et-4-MeqoH and 5- Et-4-MeqoH.HCI have shown ail three compounds to have some 1,4-oxime- imino character. The synthesis of nlckel(ll), copper(ll), palladium(ll) and platinum(ll) complexes of the acylamino and alkylamino substituted 1.2- benzoqulnone-2- oximes both by the direct and nitrosation methods was examined. The nitrosation method gave rise to complexes NI(qo)2.nH20, Cu(qo)2.nH20 and Pd(qo)2 but failed to give the corresponding platinum complexes. The latter were only obtained by the direct method. The nickel(ll) and oopper(ll) complexes reacted with pyridine and 2,2-dlpyrldyl to give adducts of the type NI(qo)2(py)2 Cu(qo) (py) and M(qo) (dipy) respectively. The palladium and platinum complexes however failed to react with either of the Lewis bases. Magnetic moment studies showed the hydrated complexes and Lewis base adducts to be magnetically dilute and thus monomeric. Such studies, as well as IR and LSIMS mass spectral analysis of the anhydrous complexes Ni(qo) and Cu(qo) , showed them to be associated both in the solid State and in solution. The reaction of selected 1,2-quinone monooximes (qoH) and metal 1.2- quinone monooximates (M(qo)2; qoH = 1,2-nap ht hoqu I none-1-oxime (1-nqoH), 1,2-naphthoquinone-2-oxime (2-nqoH), 3-butyrylamino-1,2-benzo-quinone-2-oxime, 4-chlora-1,2-benzoquinone-2-oxlme (4-ClqoH), 4-bromo-1,2-benzoquinone-2-oxime (4-BrqoH), 5-acetylamino-1,2-benzoquinone-2-oxime (5-AcqoH), 5-hydroxy-1,2-benzoquinone-2-oxlme (5-HqoH); M = Nl and Cu) with dimethyl acetylenedicarboxylate (DMAD) was systematically examined. The reaction of 1-nqoH and 5-HqoH gave rise to nucleophile addition products cis- and trans-(0-1,2-dicarbomethoxyethenyl)-1,2-naphthoquinone-1 -oxime, trans-(0-dicarbomethoxyethenyI)-5-hydroxy-1,2-benzoquinone-2-oxime. The yields were enhanced by the presence of small amounts of alkali and alkaline earth metal chlorides. With M(1-nqo)2 and M(Buqo)2 (M = Ni, Cu) 1,4-oxazines were the only products formed. However, M(4-Clqo)2 and M(4-Brqo)2 1,4-benzoxazinones and 1,4-benzoxazines were isolated. The reaction of the structurally related 1,2-dloxlmes emd metal 1,2-dioxlmates M(dmgH)2 and M(dagH)2» (dmgH2 = dimethylglyoxime; dagH_ = 1,2-dlaminoethanedlone dIoxIme; M = NI, Cu) with DMAD was also examined. The dimethylglyoxime and its metal complexes failed to afford any adducts while the 1,2-diaminoethanedione dioxIme and its metal complexes gave nucleophilic addition products cis- and trans-bls(0-1,2-dicarboxyethenyl)-1,2-diaminoethanedione dioxime. Mechanisms for the reaction of DMAD with both the quinone monooximes and the 1,2-dioximes have been proposed.

The synthesis of novel fungicidal phosphoramidates was the main objective of the present work. Various fungitoxic substituents were included in their structure together with a trichloromethyl group which has been shown to enhance fungicidal activity in other compounds. Fourteen compounds containing the 1,1,1-trichloro-2-(diethoxyphosphinylamino)ethyl group were synthesised from the condensation product of chloral and diethyl phosphoramidate. These included one derivative which also contained the 1,1,1-trichloro-2-(bisdimethylaminophosphinyl- amino)ethyl group. Other fungitoxic substituents introduced into the molecular structure of the compounds include imidazole 1,2,4-triazole, morpholine, piperazine, dimethyldithiocarbamate, diethyldithiocarbamate, xanthate and 5,6-dihydro-2-methyl-1,4-oxathiin-3-carboxylate. Preliminary investigations were carried out into the synthesis of compounds containing the 1,1,1-trichloro-2-(bisdimethylaminophosphinyl- amino)ethyl group via the condensation of chloral with N,N,N',N'-tetramethyIphosphoric triamide but these proved to be unfruitful due to side reactions. Similar side reactions occurred, but to a lesser extent, when chloral was condensed with 0-ethyl N, N-dimethylphosphorodiamidate, and one derivative was prepared containing the 1,1,1-trichloro-2-(ethoxydimethylaminophosphinylamino)ethyl group. The fifteen potential fungicides were characterised by elemental analysis, nuclear magnetic resonance spectrometry, mass spectrometry, and infra-red spectroscopy. Their fungicidal activity was assessed in vitro against spores of Fusarium culmorum, Fusarium oxysporum, Helminthosporium sativum, Helminthosporium avenge, Septoria nodorum, Ophiobolus graminis, Piricularia oryzoe and Rhizoctania solani and in vivo against Dreschlera teres and Septoria nodorum. These pathogens were chosen because they affect economically important crops, mainly wheat and barley or, in the case of P. oryzae, rice. All the compounds showed some fungicidal activity, the best results being shown by 0,0-diethyl-N-2,2,2-trlchloro-1-(dimethylthiocarbamoylthio)ethyl phosphoramidate against Fusarium culmorum.

The preparations of quadridentate macrocyclic ligands with N4-, O2N2- and S2N2-donor-sets are described.

A range of organophosphorus compounds with bicyclic and tricyclic cage structures has been prepared and studied by n.m.r. spectroscopy.

Several complexes of lithium derived from 1,2-naphthoquinone 1-oxime and 1,2-naphthoquinone 2-oxime have been prepared and characterised using analytical, spectroscopic and thermal gravimetric techniques. I.r. studies indicate that the ligands in these complexes are essentially quinoneoximic in character. For the complex Li(1-nqo)(1-nqoH).Eton the quinoneoximic character has been confirmed by X-ray crystallography. All the lithium complexes were found to be stable towards atmospheric oxygen and water. Their reactivity towards dimethylacetylene dicarboxylate was investigated and compared to that of the copper quinoneoximato complexes. Each of the lithium complexes reacted readily with the acetylene dicarboxylate to give a novel nucleophilic addition product isomeric to the Diels-Alder adduct (1,4-oxazine) obtained from the copper complexes. Re-examination of the behaviour of the copper quinoneoximato complexes towards dimethylacetylene dicarboxylate has given an insight to the mechanism of the reaction and has shown that the copper complexes also act as catalysts in the conversion of 1,4-oxazine derivatives to 1,3-oxazoles. Several lithium carboxylato and dithiocarbamato complexes have been prepared. For the dithiocarbamato complexes a new synthetic method involving the reaction of carbon disulphide and the amine with lithium chloride was developed during this study. Solubility studies were carried out on several complexes of types Li(RCO,), Li(R-NCS,)(R-NCSSH), Ll(nqo) and M(qo) (M = Li, Na2 K, Ni, Co) in polar and non-polar solvents. Maximum solubility was observed in pyridine, dimethylsulphoxlde and ethanol. The scintillation efficiency of pyridine, dimethylsulphoxide and ethanol was examined in commercially available scintillator mixtures and in scintillator mixtures developed during this study. The scintillation efficiency of the lithium complexes derived from the mono-oximes of 1,2-naphthoqulnone, carboxylic and dlthlocarbamlc acids was also investigated. The latter two set of complexes proved promising for loading liquid scintillation counters, when present as 'solid' in the scintillator mixture.

The complexlng behaviour of chloroglyoxine (cgH2), dichloroglyozime (dcgH2), and diaminoglyoxime (dagH2) towards copper and nickel has been studied.

The synthesis and structure of amine adducts of Cu(qo), where qoH = 1,2-naphthoquinone 1-oxime (1-nqoH), 1,2 naphthoquinone 2-oxime (2-nqoH), 4-chloro-1, 2-benzoquinone 2-oxime (4-ClqoH), 4-methyl-1, 2-benzoquinone 2-oxime (4-MeqoH) have been examined.