Ligand degradation and phosphorus scavenging in the reaction between 1,2-bis(diphenylphosphino)benzene (dppbz) and Ru6(μ6-C)(CO)17: Synthesis and X-ray structure of the edge-bridged square-pyramidal cluster HRu6(μ5-C)(μ3-P)(CO)14(dppbz)

Watson, William H.; Kandala, Srikanth; Richmond, Michael G.

doi:10.1016/j.jorganchem.2006.12.036

Cited by 15 publications

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“…The internuclear P(1)···P(2) distance of 3.094(2) Å has undergone a significant contraction, relative to that distance found in 2 , and the angles associated with the Os(1)−P(1)−C(1) (108.6(2)°), Os(1)−P(2)−C(2) (108.6(2)°), C(2)−C(1)−P(1) (116.9(3)°), and C(1)−C(2)−P(2) (117.9(3)°) linkages display values that are in excellent agreement with the idealized hybridization state of the subtended atom. The observed angle of 84.90(4)° for the P(1)−Os(1)−P(2) atoms is in keeping with the chelating nature of the ancillary dppbz ligand and the bite angle reported in the three known dppbz-chelated clusters Ir 4 (CO) 10 (dppbz), H 4 Ru 4 (CO) 10 (dppbz), and HRu 6 (μ 5 -C)(μ 3 -P)(CO) 14 (dppbz) . The remaining bond distances and angles are unremarkable and require no comment.…”

Section: Resultssupporting

confidence: 78%

Experimental and Computational Studies of the Isomerization Reactions of Bidentate Phosphine Ligands in Triosmium Clusters: Kinetics of the Rearrangements from Bridged to Chelated Isomers and X-ray Structures of the Clusters Os₃(CO)₁₀(dppbz), 1,1-Os₃(CO)₁₀(dppbzF₄), HOs₃(CO)₉[μ-1,2-PhP(C₆H₄-η¹)C₆H₄PPh₂], and HOs₃(CO)₉[μ-1,2-PhP(C₆H
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Yang³
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The diphosphine ligand 1,2-bis(diphenylphosphino)benzene (dppbz) reacts with the activated cluster 1,2-Os 3 (CO) 10 (MeCN) 2 (1) at room temperature to furnish a mixture of the triosmium clusters 1,2-Os 3 (CO) 10 (dppbz) (2) and 1,1-Os 3 (CO) 10 (dppbz) (3), along with a trace amount of the hydride cluster HOs 3 (CO) 9 [μ-1,2-PhP(C 6 H 4-η 1)C 6 H 4 PPh 2 ] (4). The dppbz-bridged cluster 2 forms as the kinetically controlled product and irreversibly transforms to the corresponding chelated isomer 3 at ambient temperature. The disposition of the dppbz ligand in 2 and 3 has been established by X-ray crystallography and 31 P NMR spectroscopy, and the kinetics for the conversion 2 f 3 have been followed by UV-vis spectroscopy in toluene over the temperature range 318-343 K. The calculated activation parameters (ΔH q = 21.6(3) kcal/mol; ΔS q =-11(1) eu) and lack of CO inhibition support an intramolecular isomerization mechanism that involves the simultaneous migration of phosphine and CO groups about the cluster polyhedron. The reaction between 1 and the fluorinated diphosphine ligand 1,2-bis(diphenylphosphino)tetrafluorobenzene (dppbzF 4) was examined under similar reaction conditions and was found to afford the chelated cluster 1,1-Os 3 (CO) 10 (dppbzF 4) (6) as the sole observable product. The absence of the expected bridged isomer 1,2-Os 3 (CO) 10 (dppbzF 4) (5) suggests that the dppbzF 4 ligand destabilizes 5, thus accounting for the rapid isomerization of 5 to 6. Near-UV irradiation of clusters 3 and 6 leads to CO loss and ortho metalation of an ancillary aryl group. The resulting hydride clusters 4 and HOs 3 (CO) 9 [μ-1,2-PhP(C 6 H 4-η 1)C 6 F 4 PPh 2 ] (7) have been isolated and fully characterized by spectroscopic and X-ray diffraction analyses. Both 4 and 7 react with added CO under mild conditions to regenerate 3 and 6, respectively, in quantitative yield. The rearrangements of bridged to chelated diphosphine complexes in this genre of decacarbonyl clusters have been investigated by DFT calculations. The computational results support a concerted process, involving the scrambling of equatorial CO and phosphine groups via a classical merry-go-round exchange scheme. The barriers computed for this mechanism agree well with those that have been measured, and steric compression within the bridged diphosphine groups of the reactants has been calculated to reduce the barrier heights for the rearrangement.

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Section: Resultssupporting

confidence: 78%

Experimental and Computational Studies of the Isomerization Reactions of Bidentate Phosphine Ligands in Triosmium Clusters: Kinetics of the Rearrangements from Bridged to Chelated Isomers and X-ray Structures of the Clusters Os₃(CO)₁₀(dppbz), 1,1-Os₃(CO)₁₀(dppbzF₄), HOs₃(CO)₉[μ-1,2-PhP(C₆H₄-η¹)C₆H₄PPh₂], and HOs₃(CO)₉[μ-1,2-PhP(C₆H
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Yang³
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“…The crystal structures of similar coordination modes of BDP in which two phosphorus atoms connect to one Ru atom in the polynuclear clusters have been observed, i.e., HRu 6 ( 5 -C)( 3 -P)(CO) 14 (BDP) (Watson et al, 2007), 1,1-H 4 Ru 4 (CO) 10 (BDP) (Nesterov et al, 2007), and the cationic trinuclear ruthenium complex [Ru 3 ( 2 -Cl) 3 ( 3 -Cl) 2 (BDP) 3 ]PF 6 (Mashima et al, 1997). Mononuclear ruthenium complexes with BDP have also been reported, i.e., Ru(CO) 3 (BDP) (Bunten et al, 2000), [CpRu(PPh 3 )(BDP)]Cl (Guan et al, 2003), CpRu(BDP)H (Guan et al, 2003), [RuCl(BDP)(cis-1,3,5-triaminocyclohexane)]Cl (Gamble et al, 2013), [Ru(2,2 0 :6 0 ,2 00 -terpyridine)(BDP)(CH 3 CN)](PF 6 ) 2 (Nakamura et al, 2014), [Ru(2,2 0 :6 0 ,2 00 -terpyridine))(BDP)(NO 2 )](PF 6 ) (Nakamura et al, 2015) and Cp*Ru(BDP)(PPh 2 ) (Sues et al, 2014).…”

Section: Database Surveymentioning

confidence: 76%

Crystal structure of [1,2-bis(diphenylphosphanyl)benzene]heptacarbonyldi-μ-hydrido-(μ₃-2,4,6-trimethylphenylphosphinidene)-triangulo-triruthenium

Kakizawa

2017

Acta Cryst E

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The title trinuclear ruthenium cluster, [Ru3(C30H24P2)(C9H11P)(CO)7(μ-H)2], has a triangular Ru3core that is capped with a mesitylphosphinidene ligand, μ3-PMes (Mes = mesityl = 2,4,6-trimethylphenyl). The 1,2-bis(diphenylphosphanyl)benzene molecule acts as a bidentate phosphine ligandviatwo P atoms connecting to a single Ru atom. The title compound crystallizes with two independent molecules in the asymmetric unit.

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“…Reaction of the carbide clusters Ru6(CO)17C with 1,2-bis(diphenylphosphino)benzene, resulted in abstraction of a phosphide ligand and opening of one Ru vertex to produce a tetrahedral Ru3P group (Figure 18). 38 The cluster BiIr3(CO)9 can undergo successive substitution reactions with PPh3 ( Figure 19) and the disubstituted version undergoes cyclometallation of one of the phenyl rings. 39 That cluster oxidatively adds HEPh3 (E = Ge, Sn) to produce BiIr3H3(CO)6(EPh3)3 ( Figure 20) These compounds further undergo benzene elimination to give the triply bridged BiIr3(CO)6{µ-EPh2}3 (Figure 20).…”

Section: Tetrahedral E(mln-1)3 Compoundsmentioning

confidence: 99%

Transition metal complexes of the naked pnictide elements

Whitmire

2018

Coordination Chemistry Reviews

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Even though transition metal compounds containing "naked" pnictide elements (E) have been known for many decades now, the chemistry of this interesting class of compound continues to provide surprises and intellectual challenges in describing new structures and interesting bonding patterns. The number of ligand sets that now support naked pnictide ligands has expanded from the traditional organometallic ligand sets to include metal alkoxides and N-heterocyclic carbene species, and complexes are known from the early transition metals to the end of the d-block. In this review, complexes are presented based on their structural similarities starting with metal-rich compounds containing isolated E atoms in a variety of coordination environments presented in order of increasing metal connectivity. Subsequently, compounds possessing Ex fragments with x ranging from 2 to 24 are presented in increasing nuclearity. Finally, structures with low ligand ratios and metal to pnictide ratios close to one are discussed, followed by compounds that have no supporting ligands and resemble metal allow fragments. Where appropriate, electron counting rules have been employed to explain observed structures and reactivity patterns. A particularly intense area of study has been the creation of inorganic-organometallic-organic polymers and frameworks based on discrete clusters with Ex fragments (2 £ x £ 6) where the Ex fragment provides a node for structure growth in combination with transition metal coordination frameworks based on Cu and Ag and suitable organic ligands. Simple oligomers, 1-dimensional polymers, 2-dimensional polymeric networks and 3-dimensional polymeric structure have all be prepared and structurally characterized. In addition to the structural data, synthetic methods are described. The review encompasses 170 references, 118 figures and nine schemes.

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Ligand degradation and phosphorus scavenging in the reaction between 1,2-bis(diphenylphosphino)benzene (dppbz) and Ru6(μ6-C)(CO)17: Synthesis and X-ray structure of the edge-bridged square-pyramidal cluster HRu6(μ5-C)(μ3-P)(CO)14(dppbz)

Cited by 15 publications

References 29 publications

Crystal structure of [1,2-bis(diphenylphosphanyl)benzene]heptacarbonyldi-μ-hydrido-(μ₃-2,4,6-trimethylphenylphosphinidene)-triangulo-triruthenium

Transition metal complexes of the naked pnictide elements

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Ligand degradation and phosphorus scavenging in the reaction between 1,2-bis(diphenylphosphino)benzene (dppbz) and Ru6(μ6-C)(CO)17: Synthesis and X-ray structure of the edge-bridged square-pyramidal cluster HRu6(μ5-C)(μ3-P)(CO)14(dppbz)

Cited by 15 publications

References 29 publications

Crystal structure of [1,2-bis(diphenylphosphanyl)benzene]heptacarbonyldi-μ-hydrido-(μ3-2,4,6-trimethylphenylphosphinidene)-triangulo-triruthenium

Transition metal complexes of the naked pnictide elements

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Crystal structure of [1,2-bis(diphenylphosphanyl)benzene]heptacarbonyldi-μ-hydrido-(μ₃-2,4,6-trimethylphenylphosphinidene)-triangulo-triruthenium