Cluster Compounds Bearing both High- and Low-Valent Transition Metal Fragments:  The Reactions of Imido Carbonyl Cluster Ru3(CO)10(μ3-NPh) with Dioxo Acetylide Complexes (C5Me5)W(O)2(CCR), R = Ph and CMeCH2

Pin, Chih-Wei; Chi, Yun; Chung, C.‐S.; Carty, Arthur J.; Peng, Shie‐Ming; Lee, Gene-Hsing

doi:10.1021/om980297y

Cited by 10 publications

(1 citation statement)

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“…Our particular focus has been on molybdenum/tungsten−iridium clusters, reactions with alkynes having afforded products involving alkyne coordination, dimerization, or C⋮C scission, generally in good to excellent yields, although there are no reports of reactions between these “very mixed” metal clusters and ethyndiyl or butadiyndiyl reagents, and only one study of metal alkynyl complex reactivity toward tungsten−iridium clusters 4a. (Note, however, that reactions of metal alkynyl complexes with metal clusters have afforded many examples of cluster expansion …”

Section: Introductionmentioning

confidence: 99%

Mixed-Metal Cluster Chemistry. 28. Core Enlargement of Tungsten−Iridium Clusters with Alkynyl, Ethyndiyl, and Butadiyndiyl Reagents

et al. 2005

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Reaction of [WIr3(mu-CO)3(CO)8(eta-C5Me5)] (1c) with [W(C[triple bond]CPh)(CO)3(eta-C5H5)] afforded the edge-bridged tetrahedral cluster [W2Ir3(mu4-eta2-C2Ph)(mu-CO)(CO)9(eta-C5H5)(eta-C5Me5)] (3) and the edge-bridged trigonal-bipyramidal cluster [W3Ir3(mu4-eta2-C2Ph)(mu-eta2-C=CHPh)(Cl)(CO)8(eta-C5Me5)(eta-C5H5)2] (4) in poor to fair yield. Cluster 3 forms by insertion of [W(C[triple bond]CPh)(CO)3(eta-C5H5)] into Ir-Ir and W-Ir bonds, accompanied by a change in coordination mode from a terminally bonded alkynyl to a mu4-eta2 alkynyl ligand. Cluster 4 contains an alkynyl ligand interacting with two iridium atoms and two tungsten atoms in a mu4-eta2 fashion, as well as a vinylidene ligand bridging a W-W bond. Reaction of [WIr3(CO)11(eta-C5H5)] (1a) or 1c with [(eta-C5H5)(CO)2 Ru(C[triple bond]C)Ru(CO)2(eta-C5H5)] afforded [Ru2WIr3(mu5-eta2-C2)(mu-CO)3(CO)7(eta-C5H5)2(eta-C5R5)] [R = H (5a), Me (5c)] in low yield, a structural study of 5a revealing a WIr3 butterfly core capped and spiked by Ru atoms; the diruthenium ethyndiyl precursor has undergone Ru-C scission, with insertion of the C2 unit into a W-Ir bond of the cluster precursor. Reaction of [W2Ir2(CO)10(eta-C5H5)2] with the diruthenium ethyndiyl reagent gave [RuW2Ir2{mu4-eta2-(C2C[triple bond]C)Ru(CO)2(eta-C5H5)}(mu-CO)2(CO)6(eta-C5H5)3] (6) in low yield, a structural study of 6 revealing a butterfly W2Ir2 unit capped by a Ru(eta-C5H5) group resulting from Ru-C scission; the terminal C2 of a new ruthenium-bound butadiyndiyl ligand has been inserted into the W-Ir bond. Reaction between 1a, [WIr3(CO)11(eta-C5H4Me)] (1b), or 1c and [(eta-C5H5)(CO)3W(C[triple bond]CC[triple bond]C)W(CO)3(eta-C5H5)] afforded [W2Ir3{mu4-eta2-(C2C[triple bond]C)W(CO)3(eta-C5H5)}(mu-CO)2(CO)2(eta-C5H5)(eta-C5R5)] [R = H (7a), Me (7c); R5 = H4Me (7b)] in good yield, a structural study of 7c revealing it to be a metallaethynyl analogue of 3.

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Section: Introductionmentioning

confidence: 99%

Mixed-Metal Cluster Chemistry. 28. Core Enlargement of Tungsten−Iridium Clusters with Alkynyl, Ethyndiyl, and Butadiyndiyl Reagents

et al. 2005

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Heterometallic Ru/Os-containing Compounds

Wong

2007

Comprehensive Organometallic Chemistry III

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Thermally induced dual P–C bond cleavage routes from the imido-capped cluster Ru3(CO)7(μ3-CO)(μ3-NPh)(bpcd): synthesis, spectroscopic properties, and X-ray diffraction structures of Ru3(CO)7(μ3-CO)(μ3-NPh)(bpcd), Ru3(CO)5(μ2-CO)2(μ3-NPh)(μ2-PPh2)[μ,η1,η1-CC(PPh2)C(O)CH2C(O)], Ru3(CO)6(μ2-CO)(μ3-NPh)(μ-PhCO)[μ2,η2,η1-PPhCC(PPh2)C(O)CH2C(O)], and Ru3(CO)9(μ3-NPh)(μ3-PPh)

Bott

Shen

Richmond

2004

Journal of Organometallic Chemistry

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The imido-capped cluster Ru 3 (CO) 9 (l 3 -CO)(l 3 -NPh) (1) reacts with the diphosphine ligand 4,5-bis(diphenylphosphino)-4-cyclopenten-1,3-dione (bpcd) to furnish both Ru 3 (CO) 7 (l 3 -CO)(l 3 -NPh)(bpcd) (2) and Ru 3 (CO) 5 (l 3 -CO)(l 3 -NPh)(bpcd) 2 (3) as the major and minor products, respectively, under thermal and Me 3 NO activation. The thermolysis of cluster 2 affords the new triruthenium compounds Ru 3 (CO) 5 (l 2 -CO) 2 (l 3 -NPh)(l 2 -PPh 2 )[l,g 1 ,g 1 -C@C(PPh 2 )C(O)CH 2 C(O)] (4), Ru 3 (CO) 6 (l 2 -CO)(l 3 -NPh)(l-PhCO)[l 2 ,g 2 ,g 1 -PPhC@C(PPh 2 )C(O)CH 2 C(O)] (5), and Ru 3 (CO) 9 (l 3 -NPh)(l 3 -PPh) (6). Compounds 2-6 have been fully characterized in solution, and the molecular structures of 2, and 4-6 have been determined. Cluster 2 exhibits a nido-NRu 3 core with a face-capping l 3 -CO and a chelating bpcd ligand that occupies an equatorial and axial site. VT 31 P NMR data indicate that the bpcd ligand in 2 undergoes a rocking motion between the equatorial and axial sites at the attached ruthenium center at elevated temperatures. Cluster 4 possesses a similar nido polyhedral core that is tethered by a bridging phosphido group and the 3e-donor moiety l 2 ,g 2 ,g 1 -C@C(PPh 2 )C(O)CH 2 C(O). The structure of 5 reveals a hypho architecture containing a single Ru-Ru bond and where the three ruthenium centers are bridged by imido and benzoyl moieties and the seven-electron donor ligand l 2 ,g 2 ,g 1 -PPhC@C(PPh 2 )C(O)CH 2 C(O), which results from the cleavage of one the P-Ph bonds of the original bpcd ligand. The 50e cluster 6 exhibits a nido polyhedral core consisting of three Ru(CO) 3 groups that are capped by a l 3 -imido and l 3 -phosphinidine unit. Cluster 6 represents the first structurally characterized example of a mixed PhN/PhP capped cluster belonging to the family of nido-Ru 3 (CO) 9 (l 3 -EPh) 2 clusters. The pertinent structural highlights associated with these clusters are discussed, and the lack of reactivity of the capping imido group with the bpcd ligand in Ru 3 (CO) 7 (l 3 -CO)(l 3 -NPh)(bpcd) during thermolysis is contrasted with the related benzylidyne-capped cluster PhCCo 3 (CO) 7 (bpcd).

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Cluster Compounds Bearing both High- and Low-Valent Transition Metal Fragments: The Reactions of Imido Carbonyl Cluster Ru₃(CO)₁₀(μ₃-NPh) with Dioxo Acetylide Complexes (C₅Me₅)W(O)₂(CCR), R = Ph and CMeCH₂

Cited by 10 publications

References 55 publications

Mixed-Metal Cluster Chemistry. 28. Core Enlargement of Tungsten−Iridium Clusters with Alkynyl, Ethyndiyl, and Butadiyndiyl Reagents

Mixed-Metal Cluster Chemistry. 28. Core Enlargement of Tungsten−Iridium Clusters with Alkynyl, Ethyndiyl, and Butadiyndiyl Reagents

Heterometallic Ru/Os-containing Compounds

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