Sintese e reatividade de complexos cis-bis(alquinila)platina(II) e clusters de ferro-platina

AUTOR(ES)
DATA DE PUBLICAÇÃO

2001

RESUMO

This thesis describes the results of the synthesis, characterisation and reactivity of cis-bis(alkynyl)platinum(II) complexes and iron-platinum clusters. The preparations of cis-bis(alkynyl)platinum(II) complexes were performed using terminal alkynes and [Pt(cod)Cl2] in reactions catalysed by copper(I) iodide. Posterior cod ligand substitution reactions gave several compounds. The products obtained were: [Pt(CCPh)2L2] {L2=cod (4a), dppf (5a), PBu3 (5c), CNBu (6), phen (7), [Fe(CO)4(m-dppm)] (8)} and cis-[Pt(CCSiEt3)2L2] { L2=cod (4b), dppf (5b)}. Addition of [Cu(NCMe)4]PF6 or AgO3SCF3 to compounds 4a, 5a and 7 in thf afforded {[PtL2(m-CCPh)2]2Cu}PF6, L2= cod (9), dppf (10), phen (11), and {[PtL2(m-CCPh)2]2Ag}O3SCF3 (12). The reactions of 5a and 8 with [Au(thf)L]X (L=PPh3, PPh2Me; X¨ = O3SCF3¨) resulted in cross-coupling products [Pt(h-PhCCCCPh)(dppf)] (17) and [Pt(h-PhCCCCPh)(m-dppm)Fe(CO)4] (18). The intermediate species [Pt{h-C(CCPh)=C(Ph)AuL}(dppf)]X were isolated. Addition of [Au(thf)L]X to 17 also afforded [Pt{h-C(CCPh)=C(Ph)AuL}(dppf)]X. A reaction cycle, that converts 5a to 17, was established by P NMR studies. The preparative chemistry of iron-platinum heterometallic clusters using [Fe(CO)4(dppm-P)] and platinum complexes was explored. The compounds obtained were: 18, [Pt(m-dppm)2Fe2(CO)6], [Pt2(CO)-(m-dppm)2Fe(CO)3], [Pt-(PPh3)(m-dppm)Fe2(CO)7], [Pt2(PPh3)(m-dppm)2Fe(CO)3], [Pt(PPh3)(m-dppm)(m-CO)Fe(CO)3], [Pt2(CNBu)2(m-dppm)Fe(CO)4], [Pt2(PPh3)2(m-dppm)Fe(CO)4] and [Pt2(CO)(PPh3)(m-dppm)Fe(CO)4]. The molecular structures of compounds 4a, 17 and [Pt2(CNBu)2(m-dppm)Fe(CO)4] were determined by X-ray diffraction studies.

ASSUNTO(S)

quimica inorganica complexos metalicos platina

ACESSO AO ARTIGO

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