Bridging versus chelating diphosphine in clusters: Isomers of Os3(CO)10(diphosphine)

Deeming, Antony J.; Donovan-Mtunzi, Susan; Kabir, Shariff E.

doi:10.1016/0022-328x(84)80667-1

Cited by 33 publications

(17 citation statements)

References 2 publications

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“…Contributions to the 1 H satellite subspectra also arise from couplings to 13 CO. In [Os 3 ( -H) 2 (CO) 10 ], the isotopomer containing one 13 CO ligand trans to the bridging hydrides accounts for ¾4.4% of the intensity of the main isotopomer and is then comparable to that of 187 Os satellites. A number of reports of hydride derivatives of metal carbonyl clusters put the trans coupling between 1 H and 13 CO in the 10-15 Hz range.…”

Section: Dmentioning

confidence: 95%

“…It has been shown that the cis-trans is preferred over the trans-trans coordination mode in these cases. 5 The crystal structure of the cis-trans isomer of [Os 3 (CO) 10 At higher temperatures the isomers are in rapid exchange, but at lower temperatures it is possible to resolve the osmium-phosphorus couplings. Also in this case the 1 J(Os,P) coupling for the cis-coordinated (in relation to the Os-Os bond carrying both of the phosphines) cluster is smaller than the coupling in the trans-coordinated equivalent system (see Table 1).…”

Section: Fluxional Systemsmentioning

confidence: 99%

“…In case (i) the expected 187 Os satellite subspectrum consists of the sum of two isotopomer-derived spectra, one containing the active osmium nucleus at site where the ligand is coordinated (yielding an A 2 X spin system) and the other in one of the two equivalent unsubstituted osmium centers (yielding an AA 0 X spin system). A representative example of this coordination mode is provided by 1,1-[Os 3 (CO) 10 (BINAP)] (4, Fig. 3), whose structure has been investigated previously by variable-temperature NMR of the 13 CO region.…”

Section: Dmentioning

confidence: 99%

“…The cluster [Os 3 ( -H) 2 (CO) 10 ] was used as a model cluster in the initial investigations, as it is readily soluble and easily synthesized. positions and the other containing the active osmium nucleus in the remote site.…”

Section: Dmentioning

confidence: 99%

“…4 A considerable amount of information is available to the cluster chemist from 1 J(Os,H) coupling constants which, after some early interest, 5 are only now beginning to be exploited. 6 Recent developments in NMR sensitivity have made it practical to observe 1 J(Os,H) satellites for species such as [Os 3 ( -H) 2 (CO) 10 ] 4 in a single transient at 500 MHz. Similarly, it is often possible to observe the J(Os,P) satellites in a few transients at high field.…”

Section: Introductionmentioning

confidence: 99%

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¹⁸⁷Os subspectra in ¹H and ³¹P{¹H} spectra of triosmium carbonyl clusters

Stchedroff

Aime

Gobetto

et al. 2001

Magnetic Reson in Chemistry

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Section: Dmentioning

confidence: 95%

Section: Fluxional Systemsmentioning

confidence: 99%

Section: Dmentioning

confidence: 99%

Section: Dmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 3 more Smart Citations

¹⁸⁷Os subspectra in ¹H and ³¹P{¹H} spectra of triosmium carbonyl clusters

Stchedroff

Aime

Gobetto

et al. 2001

Magnetic Reson in Chemistry

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Synthesis, Characterization, and Dynamic Behaviour of Triosmium Clusters Containing the Tridentate Ligand {Ph₂PCH₂CH₂}₂S (PSP)

et al. 2013

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Reaction of [Os3(CO)11(NCMe)] with bis‐diphenylphosphanylethylene sulfide, {Ph2PCH2CH2}2S (PSP), leads to the formation of [Os3(CO)11(PSP)] and [{Os3(CO)11}2(μ‐PSP)] in good yield. Similarly, treatment of [Os3(CO)10(NCMe)2] with PSP affords the cluster [Os3(CO)10(μ‐PSP)], in which the two phosphanes of the PSP ligand coordinate to different osmium atoms of the same triosmium unit. Reaction of [Os3(CO)11(PSP)] with [Os3(CO)10(NCMe)2] yields the compound 1,2‐[{Os3(CO)11}(μ3‐PSP){Os3(CO)10}] in which the thioether moiety and one of the phosphane groups of the PSP ligand are coordinated equatorially to the {Os3(CO)10} subunit. The cluster 1,2‐[{Os3(CO)11}(μ3‐PSP){Os3(CO)10}] is also formed when [Os3(CO)11(PSP)] is oxidatively decarbonylated by reaction with trimethylamine N‐oxide. The metastable cluster 1,2‐[{Os3(CO)11}(μ3‐PSP){Os3(CO)10}] undergoes slow isomerisation at room temperature to form 1,1‐[{Os3(CO)11}(μ3‐PSP){Os3(CO)10}] in which the thioether and phosphane moieties coordinate in a chelating mode to one of the {Os3(CO)10} subunits with the thioether moiety in an axial position. The dynamic behaviour of these clusters has been investigated by variable‐temperature 13C{1H} and 13P{1H} NMR spectroscopy. The solid‐state structures of [{Os3(CO)11}2(μ‐PSP)] and [Os3(CO)10(μ‐PSP)] are reported.

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