Aspects of actinide-Schiff base chemistry

(1)

http://researchspace.auckland.ac.nz ResearchSpace@Auckland

Copyright Statement

The digital copy of this thesis is protected by the Copyright Act 1994 (New Zealand).

This thesis may be consulted by you, provided you comply with the provisions of the Act and the following conditions of use:

• Any use you make of these documents or images must be for research or private study purposes only, and you may not make them available to any other person.

• Authors control the copyright of their thesis. You will recognise the author's right to be identified as the author of this thesis, and due acknowledgement will be made to the author where appropriate.

• You will obtain the author's permission before publishing any material from their thesis.

To request permissions please use the Feedback form on our webpage.

http://researchspace.auckland.ac.nz/feedback

General copyright and disclaimer

In addition to the above conditions, authors give their consent for the digital copy of their work to be used subject to the conditions specified on the Library Thesis Consent Form.

(2)

(3)

A B S T R A C T

Complexes of tetravalent uranium and thorium have been prepared with the tetradentate ligands N,N'- ethylenebis(salicylaldimine), N,N'-0-phenylenebis(sa1i- cylaldimine) and the analogous ligands containing

substituent groups in the salicylaldimine benzene rings (i.e. 3-Me0, 3-Et0, 5-C1, 5-NO2). Attempts to form bidentate salicylaldimine complexes were impeded by hydrolysis and oxidation; however, the metal complexes with N-Mesalicylaldimine, N-~tsalicylaldimine and N- phenylsalicylaldimine have been isolated. X-ray powder patterns for these complexes are reported.

X-ray structural studies have revealed the

salicylaldehyde, N-Mesalicylaldimine, N-Etsalicylaldimine and N,N1-o-phenylenebis(sa1icylaldimine) complexes of thorium to be eight co-ordinate, with the salicylaldimine complexes having distorted square antiprismatic co-

ordination and the salicylaldehyde complex displaying a dodecahedra1 configuration. U.V., visible and near-I.R.

spectra of Schiff-base complexes of thorium, uranium, thallium and lithium are also reported and discussed.

(4)

(5)

(6)

(7)

(8)

(9)

(10)

(11)

(12)

(13)

(14)

(15)

(16)

(17)

(18)

(19)

(20)

(21)

(22)

(23)

(24)

(25)

(26)

(27)

(28)

(29)

(30)

(31)

(32)

(33)

(34)

(35)

(36)

(37)

(38)

(39)

(40)

(41)

(42)

(43)

(44)

(45)

(46)

(47)

(48)

(49)

(50)

(51)

(52)

(53)

(54)

(55)

(56)

(57)

(58)

(59)

(60)

(61)

(62)

(63)

(64)

(65)

(66)

(67)

(68)

(69)

(70)

(71)

(72)

(73)

(74)

(75)

(76)

(77)

(78)

(79)

(80)

(81)

(82)

(83)

(84)

(85)

(86)

(87)

(88)

(89)

(90)

(91)

(92)

(93)

(94)

(95)

(96)

(97)

(98)

(99)

(100)

(101)

(102)

(103)

(104)

(105)

(106)

(107)

(108)

(109)

(110)

(111)

(112)

(113)

(114)

(115)

(116)

(117)

(118)

(119)

(120)

(121)

(122)

(123)

(124)

(125)

(126)

(127)

(128)

(129)

(130)

(131)

(132)

(133)

(134)

(135)

(136)

(137)

(138)

(139)

(140)

(141)

(142)

(143)

(144)

(145)

(146)

(147)

(148)

(149)

(150)

(151)

(152)

(153)

(154)

(155)

(156)

(157)

(158)

(159)

(160)

(161)

(162)

(163)

(164)

(165)

(166)

(167)

(168)

(169)

(170)

(171)

(172)

(173)

(174)

(175)

(176)

(177)

(178)

(179)

(180)

(181)

(182)

(183)

(184)

(185)

(186)

(187)

(188)

(189)

(190)

(191)

(192)

(193)

(194)

(195)

(196)

(197)

(198)

(199)

(200)