Novel butterfly tungsten-osmium carbido cluster Complexes from the reaction of Os3(CO)10(NCME)2 CPW(CO)3(CH2SMe)

Gong, Jia-Huey; Tsay, Chyuan-Wu; Tu, Wen-Cheng; Chi, Yun; Peng, Shie‐Ming; Lee, Gene‐Hsiang

doi:10.1007/bf01169697

Cited by 11 publications

(5 citation statements)

References 25 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The W atom is located at a wingtip position and is coordinated by a Cp* and a CO ligand. Similar skeletal arrangement has been observed in the carbide clusters CpWRu 3 (μ 4 -C)(μ-H)(CO) 11 and CpWOs 3 (μ 4 -C)(μ-SMe)(CO) 11 and the carbonyl clusters Cp*MRu 3 (μ 4 -CO)(μ-H)(CO) 11 (M = Mo, W), with a quadruply bridging CO ligand . The carbido atom C(10), which is derived from the acetylide fragment in 1 , is bound to the cluster with short M(wingtip)−C distances (average 1.96(4) Å) and long M(hinge)−C distances (average 2.17 (4) Å), typical for such a carbide in the butterfly environment .…”

Section: Resultssupporting

confidence: 60%

Reversible C−C Bond Cleavage and Interconversion of the Resulting Hydrocarbyl Ligands on Butterfly Frameworks Derived from Acetylide Complexes Cp*WOs₃(μ₄-CCR)(CO)₁₁(R = Ph,ⁿBu, CH₂OMe, CH₂OPh)

et al. 1997

Self Cite

View full text Add to dashboard Cite

Combination of mononuclear complexes Cp*W(CO) 3 (CCR) (Cp* ) C 5 Me 5 ; R ) Ph, n Bu, CH 2 OMe, CH 2 OPh) with the triosmium cluster Os 3 (CO) 10 (NCMe) 2 in toluene affords two isomeric acetylide cluster compounds a and b, which possess the formula Cp*WOs 3 (CCR)(CO) 11 (R ) Ph (1), n Bu (2), CH 2 OMe (3), CH 2 OPh (4)). Isomers a and b undergo reversible interconversion by relocating the Cp*W(CO) 2 fragment between the hinge and wingtip positions upon heating in solution. Their reactivities vs the substituents on the acetylide ligand are also investigated and compared. Thus, thermolysis of 1a furnishes the carbidoalkylidyne cluster Cp*WOs 3 (µ 4 -C)(µ-CPh)(CO) 10 ( 5) through reversible scission of the C-C bond induced by elimination of CO. By contrast, heating of 2 or 3 gives an isomeric mixture of the carbido-vinylidene clusters Cp*WOs 3 (µ 4 -C)(µ-H)(µ-CCHR′)(CO) 9 (R′ ) n Pr (6), OMe ( 7)) through a subsequent C-H activation. The CH 2 OPh isomers 4 readily eliminate two CO ligands to give two isomeric carbido-benzofuryl clusters Cp*WOs 3 (µ 4 -C)(µ-H) 2 (µ-C 8 H 6 O)-(CO) 9 (9 and 10), in which the furyl fragments are produced through subsequent orthometalation involving the phenyl group, C-C bond formation, and H migration. Hydrogenation of 3 produces the dihydrido-acetylide cluster Cp*WOs 3 (µ-H) 2 (CCCH 2 OMe)(CO) 10 ( 11) and the carbido-alkylidyne cluster Cp*WOs 3 (µ 4 -C)(µ-H) 2 (µ-CCH 2 OMe)(CO) 9 (13) subsequently. The acetylide cluster 11 converts to the tetrahedral alkylidyne complex Cp*WOs 3 (µ 3 -CCH 2 CH 2 OMe)(CO) 11 (12) via addition of a CO ligand, whereas the alkylidyne cluster 13 isomerizes upon further heating in solution, giving the alkenyl cluster Cp*WOs 3 (µ 4 -C)(µ-H) 2 (µ-CHCHOMe)(CO) 9 (14) via a 1,2-H shift. Spectroscopic data, X-ray structural analyses, and the possible mechanism leading to the interconversions are presented.

show abstract

Section: Resultssupporting

confidence: 60%

Reversible C−C Bond Cleavage and Interconversion of the Resulting Hydrocarbyl Ligands on Butterfly Frameworks Derived from Acetylide Complexes Cp*WOs₃(μ₄-CCR)(CO)₁₁(R = Ph,ⁿBu, CH₂OMe, CH₂OPh)

et al. 1997

Self Cite

View full text Add to dashboard Cite

show abstract

“…The most important features of 5 are the carbide and alkylidyne ligands which are separated by a distance (3.13(1) Å). The carbide atom C(10) occupied the Ru 2 W 2 butterfly crater; the environment around the carbide atom is analogous to that of the tetranuclear carbide clusters reported in the literature . On the other hand, the alkylidyne ligand lies on the adjacent RuW 2 metal triangle in a virtually symmetrical fashion, W(2)−C(11) = 2.128(8) Å, W(3)−C(11) = 2.104(8) Å, and Ru(2)−C(11) = 2.120(7) Å.…”

Section: Resultsmentioning

confidence: 51%

“…On the other hand, the alkylidyne ligand lies on the adjacent RuW 2 metal triangle in a virtually symmetrical fashion, W(2)−C(11) = 2.128(8) Å, W(3)−C(11) = 2.104(8) Å, and Ru(2)−C(11) = 2.120(7) Å. Its bonding is akin to that of the alkylidyne clusters LWM 3 (μ 3 -CR)(CO) 11 , L = Cp, Cp*; M = Os, Ru; R = H, Ph, OMe. 16e, In these alkylidyne complexes, the face-capping alkylidyne ligand and the edge-bridging CO ligand are all connected to the common LW(CO) 2 vertex. Moreover, the hexagonal face of phenyl substituent appears to possess some contact with two neighboring Cp* ligands.…”

Section: Resultsmentioning

confidence: 99%

Competitive Acetylide C−C Bond Scission vs Formation of a Quadruply Bridging Carbonyl Ligand. X-ray Crystal Structures of the Two Pentanuclear Clusters Cp₃W₃Ru₂(μ₄-C)(μ₃-CPh)(CO)₉ and Cp₃W₃Ru₂(μ₃-CCBu^t)(CO)₉

Chi

et al. 1997

Organometallics

Self Cite

View full text Add to dashboard Cite

Reactions of Cp*WRu 2 (CCPh)(CO) 8 (1a) with excess Cp*W(CO) 3 H, Cp* ) C 5 Me 5 , affords a carbido-alkylidyne cluster Cp* 3 W 3 Ru 2 (µ 4 -C)(µ 3 -CPh)(CO) 9 (5) alone with three byproducts, which are identified as hydride cluster Cp*WRu 3 (µ-H) 3 (CO) 11 (2), vinylidene cluster Cp* 2 W 2 -Ru 2 (CCHPh)(CO) 9 (4), and a pentanuclear oxo-carbido cluster Cp* 2 W 2 (O)Ru 3 (µ 5 -C)(CO) 11 (3). In contrast, the respective condensation using tert-butyl derivative Cp*WRu 2 -(CCBu t )(CO) 8 (1b) gives an acetylide cluster Cp* 3 W 3 Ru 2 (µ 3 -CCBu t )(CO) 9 (6). The X-ray structural determinations of 5 and 6 reveals the existence of an edge-bridged tetrahedral core, in which the butterfly crater is occupied by a µ 4 -carbide in 5 or a quadruply bridging CO ligand in 6. A plausible mechanism leading to the formation of these two cluster compounds is also presented.Transition metal clusters containing unsaturated alkyne or acetylide fragments have been an area of intense investigation due to their unique physical and chemical properties 1,2 and their relevance to the transformation of small hydrocarbyl intermediates on metal surfaces. Much work has been devoted to the development of this chemistry in recent years. For example, Carty and co-workers reported the syntheses and crystal structures of phosphido ruthenium clusters containing multisite bound acetylide ligands. 3 Adams and coworkers focused on the hydrogenation of alkyne on the layer-segregated, face-shared bioctahedral clusters. 4 Other investigations, such as the studies on the ruthenium and osmium clusters 5 and the heterometallic counterparts, 6 all provided substantial knowledge about the bonding and reactivity of cluster-bound alkyne and acetylide ligands.A much less disclosed pattern of reactivity for such complexes is the C-C bond cleavage, which affords two alkylidyne ligands from the coordinated alkynes. 7 Likewise, the related acetylide ligand, which can be envis-aged as a carbide-alkylidyne in certain polynuclear systems, 8 has been observed to convert to the wellseparated carbide and alkylidyne ligands. 9 In this article, we focus on the irreversible acetylide cleavage through the generation of a Ru 2 W 3 mixed-metal cluster, which offers an opportunity to reveal the essence of the acetylide scission vs the competing process involving the generation of the quadruply bridging CO ligand. 10 In addition, this study supplements our previous report on the reversible acetylide cleavage between the parent acetylide cluster CpWRu 2 (CCPh)(CO) 8 and the polynuclear carbido alkylidyne derivatives CpWRu 4 (µ 5 -C)-(µ-CPh)(CO) 12 and CpWRu 5 (µ 6 -C)(µ-CPh)(CO) 14 , which is also promoted by a cluster building reaction. 11

show abstract

“…Among this second group are the long-known “butterfly”-based clusters containing a linear M–C–M arrangement (i.e., with one broken M–M bond) with an exposed C atom, and a few M 4 (μ 4 -C) clusters with two or three highly elongated or broken M–M bonds. Examples are a pentametal-bonded butterfly WOs 3 (μ 4 -C) cluster of formula WOs 3 (μ 4 -C)(μ 2 -H) 2 (η 5 -C 5 H 5 )(CO) 9 (μ 2 -SMe) with a linear W–C–Os architecture, another tetrametal-bonded WOs 3 (μ 4 -C) cluster of formula WOs 3 (μ 4 -C)(η 5 -C 5 H 5 )(CO) 11 (μ 2 -SMe) with nonbonding W···Os and Os···Os distances, and a trimetal-bonded RuCo 3 (μ 4 -C) cluster with a tetrahedral sp 3 carbide atom. This latter RuCo 3 (μ 4 -C)(η 5 -C 5 H 5 )(CO) 8 L 3 cluster is the first crystallographic example of a tetrahedral sp 3 carbide cluster with the (μ 4 -C) atom coordinated to a trimetal-bonded Co 3 (CO) 6 L 3 fragment [where L 3 denotes tdpm CH(PPh 2 ) 3 ] and to an otherwise nonbonded Ru(η 5 -C 5 H 5 )(CO) 2 moiety.…”

Section: Resultsmentioning

confidence: 99%

Nanosized {Pd₄(μ₄-C)}Pd₃₂(CO)₂₈(PMe₃)₁₄Containing Tetrahedrally Deformed Pd₄Cage with Encapsulated Carbide Atom: Formal Substitution of Geometrically Analogous Interior Au₄Entity in Isostructural Au₄Pd₃₂(CO)₂₈(PMe₃)₁₄by Electronically Equivalent Pd₄(μ₄-C) and Computational/Catalytic Implications

2015

View full text Add to dashboard Cite

This first homopalladium carbido cluster, {Pd4(μ4-C)}Pd32(CO)28(PMe3)14 (1), was isolated (3-7% yields) from an ultimately simplified procedure-the reaction of CHCl3 under N2 with either Pd8(CO)8(PMe3)7 or Pd10(CO)12(PMe3)6 at room temperature. Charge-coupled device (CCD) X-ray diffraction data at 100 K for 1·2.5 C6H14 (1a) and 1·3 CHCl3 (1b) produced closely related molecular parameters for 1. This {Pd4C}Pd32 cluster (1) possesses a highly unusual tetracoordinated carbide atom that causes a major distortion of a central regular Pd4 tetrahedron into a new symmetry type of encapsulated Pd4 cage of pseudo-D2 (222) symmetry. Mean Pd-Pd distances for the three pairs of opposite twofold-equivalent Pd-Pd tetrahedral-like edges for 1a are 2.71, 2.96, and 3.59 Å; the mean of the four Pd-C distances [range, 1.87(2)-1.94(2) Å] is 1.91 Å. An astonishing molecular feature is that this {Pd4C}Pd32 cluster (1) is an isostructural and electronically equivalent analogue of the nanosized Au4Pd32(CO)28(PMe3)14 (2). Cluster 2, likewise a pseudo-D2 molecule, contains a geometrically analogous tetrahedrally deformed interior Au4 entity encapsulated within an identical Pd32(CO)28(PMe3)14 shell; mean distances for the three corresponding symmetry-equivalent pairs of slightly smaller opposite tetrahedral-distorted Au-Au edges are 2.64, 2.90, and 3.51 Å. A computational study by both a natural population analysis (NPA) and an atoms-in-molecules (AIM) method performed on model analogues {Pd4C}Pd32(CO)28(PH3)14 (1-mod) and Au4Pd32(CO)28(PH3)14 (2-mod) suggested that the negatively charged Au4 entity in 2-mod may be described as two weakly interacting electron-pair Au2 intradimers. In contrast, an NPA of the {Pd4C} entity in 1-mod revealed that two similarly oriented identical Pd2 intradimers of 2.71 Å are primarily stabilized by Pd-C bonding with a negatively charged carbide atom. The isostructural stabilizations of 1 and 2 are then attributed to the similar sizes, shapes, and overall negative charge distributions of the electronically equivalent interior {Pd4C} and Au4 entities. This resulting remarkable structural/electronic equivalency between 1 and 2 is consistent with the greatly improved performances of commercial palladium catalysts for vinyl acetate synthesis by gold-atom incorporation to suppress carbonization of the Pd atoms, namely, that the extra Au 6s(1) valence electron of each added Au atom provides an effective "negative charge protection" against electron-donating carbon atoms forming Pd carbido species such as {Pd4C}.

show abstract

Novel butterfly tungsten-osmium carbido cluster Complexes from the reaction of Os3(CO)10(NCME)2 CPW(CO)3(CH2SMe)

Cited by 11 publications

References 25 publications

Reversible C−C Bond Cleavage and Interconversion of the Resulting Hydrocarbyl Ligands on Butterfly Frameworks Derived from Acetylide Complexes Cp*WOs₃(μ₄-CCR)(CO)₁₁(R = Ph,ⁿBu, CH₂OMe, CH₂OPh)

Reversible C−C Bond Cleavage and Interconversion of the Resulting Hydrocarbyl Ligands on Butterfly Frameworks Derived from Acetylide Complexes Cp*WOs₃(μ₄-CCR)(CO)₁₁(R = Ph,ⁿBu, CH₂OMe, CH₂OPh)

Competitive Acetylide C−C Bond Scission vs Formation of a Quadruply Bridging Carbonyl Ligand. X-ray Crystal Structures of the Two Pentanuclear Clusters Cp₃W₃Ru₂(μ₄-C)(μ₃-CPh)(CO)₉ and Cp₃W₃Ru₂(μ₃-CCBu^t)(CO)₉

Contact Info

Product

Resources

About

Novel butterfly tungsten-osmium carbido cluster Complexes from the reaction of Os3(CO)10(NCME)2 CPW(CO)3(CH2SMe)

Cited by 11 publications

References 25 publications

Reversible C−C Bond Cleavage and Interconversion of the Resulting Hydrocarbyl Ligands on Butterfly Frameworks Derived from Acetylide Complexes Cp*WOs3(μ4-CCR)(CO)11(R = Ph,nBu, CH2OMe, CH2OPh)

Reversible C−C Bond Cleavage and Interconversion of the Resulting Hydrocarbyl Ligands on Butterfly Frameworks Derived from Acetylide Complexes Cp*WOs3(μ4-CCR)(CO)11(R = Ph,nBu, CH2OMe, CH2OPh)

Competitive Acetylide C−C Bond Scission vs Formation of a Quadruply Bridging Carbonyl Ligand. X-ray Crystal Structures of the Two Pentanuclear Clusters Cp*3W3Ru2(μ4-C)(μ3-CPh)(CO)9 and Cp*3W3Ru2(μ3-CCBut)(CO)9

Nanosized {Pd4(μ4-C)}Pd32(CO)28(PMe3)14Containing Tetrahedrally Deformed Pd4Cage with Encapsulated Carbide Atom: Formal Substitution of Geometrically Analogous Interior Au4Entity in Isostructural Au4Pd32(CO)28(PMe3)14by Electronically Equivalent Pd4(μ4-C) and Computational/Catalytic Implications

Contact Info

Product

Resources

About

Reversible C−C Bond Cleavage and Interconversion of the Resulting Hydrocarbyl Ligands on Butterfly Frameworks Derived from Acetylide Complexes Cp*WOs₃(μ₄-CCR)(CO)₁₁(R = Ph,ⁿBu, CH₂OMe, CH₂OPh)

Reversible C−C Bond Cleavage and Interconversion of the Resulting Hydrocarbyl Ligands on Butterfly Frameworks Derived from Acetylide Complexes Cp*WOs₃(μ₄-CCR)(CO)₁₁(R = Ph,ⁿBu, CH₂OMe, CH₂OPh)

Competitive Acetylide C−C Bond Scission vs Formation of a Quadruply Bridging Carbonyl Ligand. X-ray Crystal Structures of the Two Pentanuclear Clusters Cp₃W₃Ru₂(μ₄-C)(μ₃-CPh)(CO)₉ and Cp₃W₃Ru₂(μ₃-CCBu^t)(CO)₉