Synthesis, crystal structure and some reactions of the ruthenacarborane complex [Ru(CO)2(MeCCPh)(η5-7,8-C2B9H11],

Jeffery, John C.; Jelliss, Paul A.; Psillakis, Elefteria; Rudd, Gillian; Stone, F. Gordon A.

doi:10.1016/s0022-328x(98)00363-5

Cited by 30 publications

(8 citation statements)

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“…When the search is restricted to only {3,1,2‐ closo ‐MC 2 B 9 H 11 } fragments to minimise the possible influence of intramolecular steric crowding on conformation, there is only one [(CO)(PPh 3 ) 2 MC 2 B 9 H 11 ] species, [3‐CO‐3,3‐(PPh 3 ) 2 ‐3,1,2‐ closo ‐RuC 2 B 9 H 11 ] ( BIHQUE ), and one [(CO) 2 (PPh 3 )MC 2 B 9 H 11 ] species, [3,3‐(CO) 2 ‐3‐PPh 3 ‐3,1,2‐ closo ‐FeC 2 B 9 H 11 ] ( KISBIX ), in the Cambridge Structural Database (CSD) . Key ELO data for these, together with those of the closely related species [3‐µ‐(PPh 2 CH 2 PPh 2 )‐{3,3‐(CO) 2 ‐3,1,2‐ closo ‐RuC 2 B 9 H 11 } 2 ] ( HIZQUC ), are presented in Tables and .…”

Section: Resultsmentioning

confidence: 99%

Balancing Steric and Electronic Effects in Carbonyl–Phosphine Molybdacarboranes

et al. 2017

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Analysis of the literature structures [(CO)(PPh3)2MC2B9H11] and [(CO)2(PPh3)MC2B9H11] suggests that in [L3MC2B9H11] metallacarboranes the trans influence of CO is greater than that of PPh3. Extending this study to the [L4MC2B9H11] system the new molybdacarboranes [3,3,3‐(CO)3‐3‐PPh3‐3,1,2‐closo‐MoC2B9H11] (2), [1,2‐Me2‐3,3,3‐(CO)3‐3‐PPh3‐3,1,2‐closo‐MoC2B9H9] (3) and trans‐[3,3‐(CO)2‐3,3‐(PPh3)2‐3,1,2‐closo‐MoC2B9H11] (4) were prepared and fully characterised. Consideration of the exopolyhedral ligand orientations (ELO) in 2 confirms that, in terms of trans influence, CO > PPh3 in [L4MC2B9H11] also. The ELO is effectively reversed in 3 through intramolecular steric crowding between the cage CH3 groups and the PPh3 ligand. The dicarbonylbis(triphenylphosphine) compound 4 has effective Cs symmetry with one CO ligand trans and the other CO ligand cis to the cage C–C connectivity. Unexpectedly the Mo–CO bond lengths are equal. DFT calculations on 4 reproduce this unusual result, but suggest that in the less‐crowded PH3 analogue, the Mo–CO bond length trans to cage C would be about 0.2 Å shorter than that trans to cage B. To test this prediction, the analogous PEt3 complex was prepared as cis and trans structural isomers 5 and 6. The cis isomer 5 is quantitatively converted into the trans isomer 6 when heated to reflux in THF. In 6 the Mo–CO bond more trans to cage C is about 0.2 Å shorter than that which is more trans to cage B, in line with the DFT prediction.

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Section: Resultsmentioning

confidence: 99%

Balancing Steric and Electronic Effects in Carbonyl–Phosphine Molybdacarboranes

et al. 2017

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“…(1) with 1,5-bis(diphenylphosphino)pentane (2) in benzene either at ambient temperature for ca 2 days or under gently reflux for 30 min in anaerobic conditions both proceed with the replacement of PPh 3 ligands on the ruthenium center with the diphosphine to form diamagnetic (18-electron) closo complex [3,3-{k 2 -{Ph 2 P(CH 2 ) 5 PPh 2 }}-3-Cl-3-H-closo-3,1,2-RuC 2 B 9 H 11 ] (3). On heating in benzene, 3 in the presence of a small amount of CCl 4 affords stable paramagnetic (17-electron) species [3,3-{k 2 -{Ph 2 P(CH 2 ) 5 PPh 2 }}-3-Clcloso-3,1,2-RuC 2 B 9 H 11 ] (5) along with traces of ortho-phenylenecycloboronated closo complex, (7).…”

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confidence: 99%

Mononuclear closo-ruthenacarborane complexes containing a rare eight-membered metal-diphosphine ring

Гришин¹,

D’yachihin

Turmina³

et al. 2012

Journal of Organometallic Chemistry

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“…The typical values for C c H 1 H chemical shift for closo ruthenacarboranes lie in the range from 1.5 to 3.5 ppm depending on auxiliary ligands. [19][20][21][22][23][24][25][26][27][28] At the same time the signals of protons of complexes 2-4 and 6 lie in the lower field area. The data provided in the Table 2 shows that the increase of the donating ability of alkyl substituent in complexes 3, 4, 6 (methyl, ethyl, tert.-butyl) results in a shielding of the C c À H resonances.…”

Section: Resultsmentioning

confidence: 94%

Synthesis of Novel Pseudocloso Ruthenacarboranes based on an Unsubstituted nido‐C₂B₉H₁₁²⁻ Ligand

et al. 2021

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The reaction of the known closo-ruthenacarborane 3-H-3-Cl-3,3-(PPh 3 ) 2 -closo-3,1,2-RuC 2 B 9 H 11 with tridentade nitrogen-based ligands of the general formula (C 5 NH 4 CH 2 ) 2 NR (R=H, Me, Et, iPr, Bu t ) in benzene solution at 60 °C allowed us to isolate novel ruthenacarborane clusters 3,3,3-(2'-NC 5 H 4 CH 2 ) 2 NR-pseudocloso-3,1,2-RuC 2 B 9 H 11 . According to the performed X-ray study, the obtained compounds are the first examples of pseudoclosometallacarboranes bearing unsubstituted C 2 B 9 2À nido-carborane ligand. In spite of the determined pseudocloso structure of the complexes in the solid state, the recorded 11 B{ 1 H} NMR spectra indicate that some of them are converted into the closo isomers in solution. The conducted quantum-chemical calculations have confirmed the subtle difference between two configurations and possible rearrangement in solution. The performed electrochemical investigations show the ability of the formed ruthenacarboranes to undergo reversible oxidation to Ru(III) species.

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Synthesis, crystal structure and some reactions of the ruthenacarborane complex [Ru(CO)2(MeCCPh)(η5-7,8-C2B9H11],

Cited by 30 publications

References 13 publications

Balancing Steric and Electronic Effects in Carbonyl–Phosphine Molybdacarboranes

Balancing Steric and Electronic Effects in Carbonyl–Phosphine Molybdacarboranes

Mononuclear closo-ruthenacarborane complexes containing a rare eight-membered metal-diphosphine ring

Synthesis of Novel Pseudocloso Ruthenacarboranes based on an Unsubstituted nido‐C₂B₉H₁₁²⁻ Ligand

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Synthesis, crystal structure and some reactions of the ruthenacarborane complex [Ru(CO)2(MeCCPh)(η5-7,8-C2B9H11],

Cited by 30 publications

References 13 publications

Balancing Steric and Electronic Effects in Carbonyl–Phosphine Molybdacarboranes

Balancing Steric and Electronic Effects in Carbonyl–Phosphine Molybdacarboranes

Mononuclear closo-ruthenacarborane complexes containing a rare eight-membered metal-diphosphine ring

Synthesis of Novel Pseudocloso Ruthenacarboranes based on an Unsubstituted nido‐C2B9H112− Ligand

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Synthesis of Novel Pseudocloso Ruthenacarboranes based on an Unsubstituted nido‐C₂B₉H₁₁²⁻ Ligand