Please use this identifier to cite or link to this item: http://scholarbank.nus.edu.sg/handle/10635/15380
Title: Synthesis and reactivity studies of cyclopentadienyl derivatives of ruthenium-iridium and osmium-iridium mixed metal clusters
Authors: SRINIVASAN PADMAMALINI
Keywords: Osmium; Ruthenium; Iridium; clusters; alkynes; substitution
Issue Date: 25-May-2006
Source: SRINIVASAN PADMAMALINI (2006-05-25). Synthesis and reactivity studies of cyclopentadienyl derivatives of ruthenium-iridium and osmium-iridium mixed metal clusters. ScholarBank@NUS Repository.
Abstract: The cyclopentadienyl-containing ruthenium-iridium and osmium-iridium mixed metal clusters Cp*IrRu3(i?--H)2(CO)10, 3a, Cp*IrRu3(i?--H)4(CO)9, 4a, CpIrRu3(i?--H)2(CO)10, 3b, Cp*IrOs3(i?--H)2(CO)10, 3c, Cp*IrOs4(i?--H)2(CO)13, 7 and Cp*IrOs3(i?--H)4(CO)9, 4b have been synthesized and characterized. Reaction of cluster 3a at elevated temperatures and 4b in the presence of excess triethylamine towards alkynes (RCCRa??) afforded butterfly clusters of the general formulae Cp*IrM3(CO)9(RCCRa??), where M = Ru, Os. Substitution reactions of 3c under TMNO activation with group 15 substrates gave the monosubstituted and disubstituted derivatives, Cp*IrOs3(i?--H)2(CO)9(L) (where L = PPh3, P(OMe)3, tBuNC, CyNC or py), and Cp*IrOs3(i?--H)2(CO)8(L)2 (where L = PPh3, P(OMe)3 or tBuNC), respectively. Cluster 3c underwent oxidative-addition type reactions with group 16 substrates under chemical activation with TMNO, to afford (i) Cp*IrOs3(i?--H)3(CO)9(i?--SPh), 22, with C6H5SH, (ii) five new clusters, viz., Cp*IrOs3(i?--H)2(CO)9(i?-i??-Se), 23, Os3(i?--H)2(CO)7(i?-i??-Se)(PPh3)2, 24, Cp*IrOs3(i?--H)2(i?-i??-Se)(CO)8(PPh3), 25, Cp*IrOs3(i?--H)2(i?-i??-Se)2(CO)7(PPh3), 26, and Cp*IrOs3(i?--H)2(CO)9(PPh3), 17a, with Ph3PSe, and (iii) three isomeric clusters, 27 - 29, of formula Cp*IrOs3(i?--H)2(i?--Te-p-C6H4CH3)2(CO)8, with di-p-tolyl ditelluride.
URI: http://scholarbank.nus.edu.sg/handle/10635/15380
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