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Durham e-Theses
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Some reactions of a-phenyl-1,2,3,5-dithiadiazole

Gorrell, Ian Barnes (1989) Some reactions of a-phenyl-1,2,3,5-dithiadiazole. Doctoral thesis, Durham University.



The reactivity of the above compound, hereafter referred to as phenyl dithiadiazole, (PhCN(_2)S(_2))(_2), toward the following transition metal carbonyl species has been investigated: V(CO)(_6), Mo(CO)(_6), W(CO)(_6), Mn(_2)(CO)(_10), Re(_2)(CO)(_10). Fe(CO)(_5), Fe(_2)(CO)(_9), Fe(_3)(CO)(_12), Co(_2)(CO)(_8), CpV(_CO)(_4), [CpMo(CO)(_3)](_2), CpMn(CO)(_3), [CpFe(CO)(_2)](_2), CpCo(CO)(_2) and the following new compounds characterised: Mn(_2)(CO)(_8)PhCN(_2)S(_2), Fe(_2)(CO)(_6)PhCN(_2)S(_2)*, [CpV(PhCN(_2)S(_2)](_2), [CpCo(PhCN(_2)S)](_2) and Cp(_2)Ni(_2)(PhCN(_2)S(_2))*; those marked with an asterisk by X-ray analysis (W Clegg). Reactivity studies of (PhCN(_2)S(_2))(_2) with the following transition metal phosphine and halogeno- compounds were also carried out: MC1(_2) (M=Cr,Mn,Co,Ni,Pd,Cu), FeBr(_2), TiC1(_4)(+Mg), Cp(_2)TiC1(_2)(+Mg) and NiC1(_2)(+Mg). MoC1(_4)(CH(_3)CN)(_2), CuC1, (Ph(_3)P)(_4)M (M=Pd,Pt) and (Ph(_3)P)(_3)RhC1 and the following new complexes prepared: [PhCN(_2)S(_2)](_2)PdC1(_4), [PhCN(_2)S(_2))(_2)CuC1(_2), PhCN(_2)S(_2)(CuC1)(_2). (Ph(_3)P)(_2)M(PhCN(_2)S(_2))(_2) (M=Pd,Pt) and [(Ph(_3)P)Pt(PhCN(_2)S)](_2). Also, the reactivity of phenyl dithiadiazole toward R(_3)P (R=Ph.Me), Ph(_3)As, S(_8), M(_3)NO, N(_3)(^-), Me(_n)NH(_3)(_-n) (n=0-3), MeX (X=I,OSO(_2)F). MeCOBr, Me(_3)SiX (X=C1,Br), HX (X=C1,BF(_4)), NO, N(_2)O(_4), N(_2)F^, (Me(_3)Sn)(_2), AgF(_2) and TCNQ has been studied and gave rise to the following novel species: [PhC(NHMe)(_2)](_2)S(_6), [PhC(NH(_2))(_2)][S(_2)N(_3)S., [PhC(NH)(_2)s(_2)]X (X=C1,BF(_4)), [PhCN(_2)S(_2)]SO(_2)F(_3). [PhCN(_2)S(_2)](_3)F. PhCN(_2)S(_2)F and PhCN(_2)S(_2)(TCNQ)(_2). Finally,[MoC1(_2)(PhCN(_2)S(_2))(thf)](_2) and [Na(C(_12)H(_24)O(_6))]PhCN(_2)S(_2) are reported as are the unusual magnetic properties of some of the above transition-metal complexes.

Item Type:Thesis (Doctoral)
Award:Doctor of Philosophy
Thesis Date:1989
Copyright:Copyright of this thesis is held by the author
Deposited On:08 Feb 2013 13:38

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