Shane A. MacLaughlin

Open and closed ruthenium and osmium clusters with μ3-acetylide and phosphido bridges

Abstract The synthesis and structural characterisation of “open” M 3 (CO) 9 (CCR)(PPh 2 ) (M = Ru, Os; R = i-Pr, t-Bu) clusters with μ 3 -acetylides and phosphido groups bridging an “open” edge of the M 3 triangle are described. Facile conversion of Ru 3 (CO) 9 (CCR)(PPh 2 ) to “closed” Ru 3 (CO) 8 (CCR)(RPh 2 ) occurs via loss of CO and metal—metal bond formation, a process which is reversible under one atmosphere of CO.

Reactivity of unsaturated clusters. Phosphoruscarbon bond activation, hydrogen migration and acetylene interconversion in the reactions of 46-electron (H)Ru3(CO)9(μ-PPh2) with Ph2PCCR (R = Ph, But, Pri). X-ray structure of Ru3(CO)9(μ-PPh2)2(μ3-η2-HCCPh): a new type of 5-vertex, 7-skeletal pair cluster

Abstract Novel examples of PC bond activation under mild conditions are reported. The reactions of phosphinoalkynes Ph 2 PCCR (R = Ph, Bu t , Pr i ) with the formally 46-electron cluster HRu 3 (CO) 9 (μ-PPh 2 ) result in PC bond cleavage, transfer of a phosphido group onto the cluster, and transfer of hydride to the acetylide. The new species Ru 3 (CO) 7 (μ-PPh 2 ) 2 (μ 3 -η 2 -HCCR), of which the derivative with R = Ph has been studied by X-ray diffraction, are representatives of a new class of μ 2 -η 2 -| acetylene cluster with NIDO 5-vertex structures.

NiRu4(CO)9(µ-PPh2)2(µ4-CCPri)2: a pentanuclear mixed metal cluster with a novel metal framework

The synthesis of a novel pentanuclear nickel–ruthenium cluster, [NiRu4(CO)9(µ-PPh2)2(µ4-CCPri)2], via the addition of an electron-rich species [(η-C5H5)Ni(CO)]2 to a carbocationic µ3-acetylide group in [Ru3(CO)9(µ3-CCPri)(PPh2)] is described; the X-ray structural analysis has shown that the metal framework consists of a ruthenium atom butterfly with the open edge bridged by a nickel atom, and the two acetylide ligands are co-ordinated in multi-site fashion to the metal cluster.

Synthetic routes to butadienyl complexes. Double addition of methylene to an acetylide and hydrometallation of an ene–yne. X-Ray crystal structure of [Fe2(CO)5{µ-η2,η3-H2CC(Me)CCH2}(µ-PPh2)]

Binuclear butadienyl complexes [Fe2(CO)5{µ-η2,η3-H2CC(R)CCH2}(µ-PPh2)](R = But, Me) have been synthesized via double addition of CH2 fragments to an acetylide in [Fe2(CO)6(µ-η1,η2-CCBut)(µ-PPh2)] or hydrometallation of the ene–yne CH2C(Me)CCH with [HFe2(CO)7(µ-PPh2)].

Ru4(CO)10(CCHPri)(OH)(PPh2) : a tetranuclear ruthenium carbonyl cluster with µ4-vinylidene and face-bridging hydroxo-groups; X-ray crystal structures of Ru4(CO)10(CCHPri)(OR)(PPh2)(R = H or Et)

Fragmentation of Ru3(CO)11(Ph2PCCPri) in wet THF or THF–EtOH generates the tetranuclear carbonyl clusters Ru4(CO)10(CCHPr1)(OR)(PPh2)(R = H, Et) which have been shown by X-ray diffraction to consist of ‘butterfly’ arrangements of metal atoms with multi-site bound µ4-vinylidene and face-bridging OH or OR groups.

Cluster bound phosphinovinylidenes and phosphinitovinylidenes from alkynilphosphines and their oxides: synthesis and structures of [Ru3(CO)9{μ3-σ,σ,η3-CCCHMe2(PPh2)}] and [Fe3(CO)9{μ3-σ,σ,η3-CCCHMe2(Ph2PO)}]

Abstract The alkynylphosphine Ph 2 PCCCHMe 2 can be converted via the phosphido-acetylide complex Ru 3 (CO) 9 {μ 3 -σ,η 2 -CC(CHMe 2 )}(μ-PPh 2 ) to the isomeric vinylidene cluster [Ru 3 (CO) 9 {μ 3 -σ,σ,η 3 -C CCHMe 2 (P Ph 2 )}] whose structure has been determined by X-ray analysis; the oxide Ph 2 P(O)CCCHMe 2 with Fe 2 (CO) 9 afforded a structurally related cluster [Fe 3 (CO) 9 {μ 3 -σ,σ,η 3 -C CCHMe 2 (Ph 2 PO )}].