Substitution derivatives of the heteronuclear cluster RuOs3(μ-H)2(CO)13: Monosubstituted group 15 derivatives

2007

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A high‐yielding alternative synthesis of the dppm‐bridged heteronuclear cluster RuOs3(μ‐H)2(CO)9(μ‐CO)2(μ‐dppm) (1) [dppm = bis(diphenylphosphanyl)methane] has been developed. Thermolysis of 1 resulted in dephenylation of both phosphane groups to afford the butterfly cluster RuOs3(CO)12(μ4,κ2:κ2‐PhPCH2PPh) (2). The reaction of 1 with selected alkynes afforded the products RuOs3(μ‐H)(CO)8(μ‐CO)(μ3,κ2:κ1‐PhPCH2PPh2)(μ3,η1:η2:η1‐L) (3) (L = alkyne) in which the alkyne is aligned parallel to an Os–Os bond(// Os‐Os isomer). The clusters incorporating internal alkynes underwent isomerization to the //Ru‐Os isomer by alkyne and hydride migration. Several other cluster products of these reactions were also identified, including RuOs3(μ‐H)(CO)8(μ‐CO)(μ3,κ2:κ1‐PhPCH2PPh2)(μ3,η1:η2:η1‐tBuC2CHO)(6) in which the methyl group of the alkyne has been oxidized to an aldehyde. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)

The Ditertiary‐Phosphane‐Bridged Heteronuclear Cluster RuOs₃(μ‐H)₂(CO)₉(μ‐CO)₂(μ‐dppm): Synthesis and Reactivity with Alkynes

Tan

2007

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The Aromatization of C₅ Rings on a Heteronuclear Cluster

Tan

2007

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The reaction of the heteronuclear cluster RuOs3(μ‐H)2(CO)13 with saturated and unsaturated C5 rings led to the aromatization of the rings to afford the clusters RuOs3(μ‐H)(CO)9(μ‐CO)2(η5‐C5R4R′). However, the reaction with cyclopentene gave the cluster RuOs3(μ‐H)3(CO)11(μ,η1:η2‐C5H7) via C–H activation of an sp2 carbon instead. Thermolysis of two of the products, RuOs3(μ‐H)(CO)9(μ‐CO)2(η5‐Cp′) and RuOs3(μ‐H)(CO)9(μ‐CO)2(η5‐C5H4SiMe3), led to their isomerization to butterfly clusters.(© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)

Synthesis and Reactivity of Ruthenium–Antimony Carbonyl Clusters

Ganguly

et al. 2015

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The reaction of Na[HRu3(CO)11] (2) with SbPh2Cl in dry tetrahydrofuran (THF) afforded the cluster Ru3(CO)10(μ‐H)(μ‐SbPh2) (3); in dry dichloromethane (DCM), the six‐membered ring Ru6(CO)20(μ‐H)2(μ‐SbPh2)2 (4) was obtained instead. The trimethylamine N‐oxide (TMNO) activated reaction of Ru3(CO)12 (1) with distibine Sb2Ph4 produced Ru3(CO)10(μ‐SbPh2)2 (6) through an Sb–Sb bond oxidative addition. Cluster 6 is fluxional through Ru–Ru bond isomerization. In contrast, its group 15 monosubstituted derivatives Ru3(CO)9(μ‐SbPh2)2(L) (7, L = phosphane, arsine or stibine) or the disubstituted derivatives Ru3(CO)8(μ‐SbPh2)2(L)2 (8) did not exhibit such fluxionality. Instead, isomerization through a turnstile mechanism involving the group 15 ligand occurred. The treatment of 6 with SbPh2Cl afforded the fused‐ring clusters Ru3(CO)9(μ‐SbPh2)3(Cl) (9) and Ru3(CO)8(μ‐SbPh2)3(Cl)(SbPh2CH2Cl) (10).