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Title: Studies of the role of ligands in determining the structures of polynuclear metal compounds.
Author: Adatia, T.
Awarding Body: Polytechnic of North London
Current Institution: London Metropolitan University
Date of Award: 1988
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Full X-ray structure analyses ot sixteen .etal cluster compounds of nuclearity 3 to 11 have been carried out to investigate to what extent the attached surface ligands govern the structure in the solid state and how this relates to the chemistry of the cluster in solution. The structure of the tetranuclear cluster [AgRu,(CO),(CzBut)(PPh,)] has completed a series of related clusters [MRu,(CO),(CzBut)(PPh,)] [M a Cu, Ag or Au]. This is only the second example of a complete series of Group IB cluster analogues and confirms earlier evidence that the bonds fro. gold are different in character to those trom silver and copper. The structures of the copper clusters [Cu,Ru.(~,-H),(CO)'Z{P(C6H'1)'}Z] and [Cu,Ru.(~,-H)Z (CO)tZ {P(CHMel ) l} l ] compared to the reported structure [Cu,Ru"(~J-H)z(CO)tZ(PPhl)l] indicate that the 'bulk' of the organophosphine groups is a major factor in determining the type of metal geometry adopted by this type of compound in the solid state. Comparison of the structural results obtained for the hexanuclear clusters [M,Ru,,(CO).,(PPh,),] [M a Cu or Ag] to those reported for the hydrido analogues [MlRu.(~,-H)z(CO)'l(PPh')l] have shown that small changes in the surface ligand set can have marked effects on the metal geometry in the solid state, providing further evidence that the energy differences between the various structural types are small for heteronuclear clusters containing Group IB metal atoms. The X-ray structure analyses of [AulRu.(~-H)(~,-H)(CO)ll{~-Ph,PCH=CHPPhz}] and [Au,Ru,,(~-H)(CO),,{~-PhzPCH,PPhz}(PPhJ)] have enabled the correlation of earlier structural data of related hexanuclear and heptanuclear mixed-metal clusters to account tor the marked differences between the structures of gold-ruthenium clusters with monodentate organophosphines, -compared to those with bidentate phosphine ligands. The X-ray structures ot the isomers [Os,Hz(CCHOEt)(CO).l and [Os.H,(HCCOEt) (CO),] provide a rare exaaple of cluster isomers differing only in the nature of the organo ligands. The structures of the high nuclearity hydrido clusters [Os.HZ(CO)'7- P(OMe),]' [Os7HZ (CO)u], and [Os7HZ (CO)..{MeCaCMe}] have shown nove1 metal fraaeworks, supporting previous observations that when hydrido ligands are present, osmium cluster geo.etries can often be unpredictable in the solid state. The structural characterisation of the large hydrido cluster monoanions [HsOs,o(CO),.]- and [HOs"C(CO)Z7]- have provided evidence for the presence of intersU Ual hydrido ligands. Comparison of these results to those reported for related compounds supports the view that in some cases. interstitial ligands become important in preventing surface ligand. overcrowding.
Supervisor: Not available Sponsor: Not available
Qualification Name: Thesis (Ph.D.) Qualification Level: Doctoral
EThOS ID:  DOI: Not available
Keywords: Transition metal chemistry