Bis(triphenylphosphine)iminium μ-hydrido-pentadecacarbonylpentaosmate, [(Ph3P)2N]+[HOs5(CO)15]−

Guy, John J.; Sheldrick, George M.

doi:10.1107/s0567740878006494

Cited by 20 publications

(5 citation statements)

References 3 publications

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“…0.06 A longer than the other two equatorial bonds in the structure, and slightly longer than the value of 2.867(2) A for the hydride-bridged bond in the cluster anion [Os,H(CO),,] -. 17 In terms of electron counting Os(4) is formally electron poor, with 17 electrons, while either Os(2) or Os(3) may be considered as electron rich, depending on the direction of donation of the bridging hydride ligand. This electronic imbalance is partially redressed by two incipient bridging carbonyl ligands, C( 12)0( 12) and C(2 1)0(2 l), donating electron density to the electron-poor Os(4) atom [Os(4)-€(12) 12), bridges the shortest 0s-0s bond in the structure.…”

Section: (10)-(12)mentioning

confidence: 99%

Chemical activation of pentaosmium carbonyl clusters: synthesis, structure, and reactivity of [Os5(CO)15(NCMe)] and [Os5H2(CO)14(NCMe)]; crystal structures of [Os5(CO)15{P(OMe)3}] and [Os5H2(CO)14(PEt3)]

Khattar¹,

Johnson²,

Lewis³

et al. 1990

J. Chem. Soc., Dalton Trans.

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289ChemInform Abstract Simple two-electron oxidation of the cluster salt (I) gives the neutral pentanuclear cluster (III). Decarbonylation of this cluster (III) and its isoelectronic dihydrido derivative (VII) in the presence of MeCN (IV) affords the activated MeCN title complexes in which the labile acetonitrile ligand associated with one of the equatorial Os atoms can be very easily substituted by other simple two-electron P-donor ligands L1 (V) and L2 (VIII) to yield the products (VI) and (XI), respectively. The structures of the title complexes (VIa) (space group P21/c, Z=4) and (IXa) (Pbca, Z = 8) are determined by X-ray analysis (for (IX) no yields given).

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Section: (10)-(12)mentioning

confidence: 99%

Chemical activation of pentaosmium carbonyl clusters: synthesis, structure, and reactivity of [Os5(CO)15(NCMe)] and [Os5H2(CO)14(NCMe)]; crystal structures of [Os5(CO)15{P(OMe)3}] and [Os5H2(CO)14(PEt3)]

Khattar¹,

Johnson²,

Lewis³

et al. 1990

J. Chem. Soc., Dalton Trans.

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“…Thus, the equatorial Ir(3) atom is connected to two bridging groups, Ir( 1) and Ir(2) to one only: therefore, in the equatorial triangle, the system of three mutually adjacent bridging carbonyl groups, which appears almost constant in trigonal bipyramidal carbonyl clusters,10-12"4 is not present. Two bridging carbonyls, CD( 14) and CD(25), can be considered symmetric, whereas the two p-CO ligands bonded to Ir(3), CD(34) and CD(35), are clearly asymmetric, with the shorter length being toward the Fe (mean Ir-C 2.225, Fe-C 1.865 A).The metal-metal distances can be divided in three sets: Ir-Ir (mean 2.708), bridged Ir-Fe (mean 2.61 8), and unbridged Ir-Fe (2.702 A). Therefore, in this monoanion, the bridging C O ligands significantly shorten the corresponding M-M bonds.…”

mentioning

confidence: 99%

Synthesis and characterization of pentanuclear Fe–Ir carbonyl clusters. Solid-state structures of [N(PPh₃)₂]₂[FeIr₄(CO)₁₅] and [PPh₄][Fe₂Ir₃(CO)₁₄]

Pergola¹,

Garlaschelli²,

Demartin³

et al. 1989

J. Chem. Soc., Dalton Trans.

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The dianion [ Felr,( C0),,l2-can be obtained b y reduction of an equimolar mixture of [ Fe( CO),] and [Ir,(CO),,] in alcoholic NaOH and under 1 atm of carbon monoxide. The salt [N( PPh,),], [Felr,( CO),,] (1) crystallizes in the triclinic space group P i with unit-cell dimensions The mean values of the Fe-lr and Ir-lr distances are 2.648 and 2.708 A, respectively. In the derivative (1) the trigonal bipyramid is considerably elongated in the direction of the apical atoms, when compared with that in (2). This elongation is consistent with the increased number of cluster valence electrons: 76 in (1 ) and 7 2 in (2).Transition-metal clusters are attracting a great deal of interest with respect to their potential as catalysts. Particularly mixedmetal clusters are extensively studied because adjacent metal centres formed by different elements offer the possibility for co-operative reactions leading to new, more active, or more selective catalysts.' -3 Moreover, they should act as potential precursors of bimetallic heterogeneous catalysts of well defined st~icheiometry.~ The lack of an extensive work on Fe-Ir bimetallic clusters5 and recent reports on Fe-lr traditional catalysts, very selective for the production of MeOH from C O and H2,6--8 prompted us to investigate this field. In this paper we describe the synthesis, the chemical characterization, and the solid-state structures of the two new clusters [N(PPh,),], [Felr,(CO),,] (1) and(2), the first examples of Fe-lr mixedmetal carbonyl clusters. Results and DiscussionPi-epurutioi? I?f' [FeIr,(CO), 5]2 -(l).

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“…Contradictory results have been found from the different 72e – TBPs considered in this paper. While PSEPT appropriately accounts for six M–M bonding electron pairs in 1 – 4 , other TEC = 72 clusters are proved to feature nine M–M bonds in agreement with EAN rule (e.g., Os 5 clusters , ). The MO analysis points out that a basic difference between the two cases is the actual degree of involvement of d orbitals in skeletal bonding.…”

Section: Discussionmentioning

confidence: 84%

“…An example is the hypothetical species [Os 5 (CO) 15 ] 2– (experimentally unknown but optimized by DFT calculations), which consists of five L 3 M-d 8 fragments with one additional electron pair introduced by the doubly negative charge. The experimentally isolated isoelectronic [Os 5 (CO) 14 (PR 3 )(μ-H)] − and Os 5 (CO) 15 (μ-H) 2 may be formally seen as the result of protonating one or two Os–Os bonds, without changing the number of electrons, or alternatively two edge-bridging hydrides supply the electrons similarly to the Sn(II) lone pairs in 1 – 4 . At variance with the latter, H 1s orbitals are contracted and hardly withstand with a M 3 capping position, an exception being found in [Pt 3 (dppm) 3 (μ 3 -H)] + .…”

Section: Resultsmentioning

confidence: 99%

Electronic Stabilization of Trigonal Bipyramidal Clusters: the Role of the Sn(II) Ions in [Pt₅(CO)₅{Cl₂Sn(μ-OR)SnCl₂}₃]^3– (R = H, Me, Et, ⁱPr)

et al. 2011

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The new [Pt(5)(CO)(5){Cl(2)Sn(μ-OR)SnCl(2)}(3)](3-) (R = H, Me, Et, (i)Pr; 1-4) clusters contain trigonal bipyramidal (TBP) Pt(5)(CO)(5) cores, as certified by the X-ray structures of [Na(CH(3)CN)(5)][NBu(4)](2)[1]·2CH(3)CN and [PPh(4)](3)[4]·3CH(3)COCH(3). The TBP geometry, which is rare for group 10 metals, is supported by an unprecedented interpenetration with a nonbonded trigonal prism of tin atoms. By capping all the Pt(3) faces, the Sn(II) lone pairs account for both Sn-Pt and Pt-Pt bonding, as indicated by DFT and topological wave function studies. In the TBP interactions, the metals use their vacant s and p orbitals using the electrons provided by Sn atoms, hence mimicking the electronic picture of main group analogues, which obey the Wade's rule. Other metal TBP clusters with the same total electron count (TEC) of 72 are different because the skeletal bonding is largely contributed by d-d interactions (e.g., [Os(5)(CO)(14)(PR(3))(μ-H)(n)](n-2), n = 0, 1, 2). In 1-4, fully occupied d shells at the Pt(ax) atoms exert a residual nucleophilicity toward the adjacent main group Sn(II) ions permitting their hypervalency through unsual metal donation.

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Bis(triphenylphosphine)iminium μ-hydrido-pentadecacarbonylpentaosmate, [(Ph₃P)₂N]⁺[HOs₅(CO)₁₅]⁻

Cited by 20 publications

References 3 publications

Chemical activation of pentaosmium carbonyl clusters: synthesis, structure, and reactivity of [Os5(CO)15(NCMe)] and [Os5H2(CO)14(NCMe)]; crystal structures of [Os5(CO)15{P(OMe)3}] and [Os5H2(CO)14(PEt3)]

Chemical activation of pentaosmium carbonyl clusters: synthesis, structure, and reactivity of [Os5(CO)15(NCMe)] and [Os5H2(CO)14(NCMe)]; crystal structures of [Os5(CO)15{P(OMe)3}] and [Os5H2(CO)14(PEt3)]

Synthesis and characterization of pentanuclear Fe–Ir carbonyl clusters. Solid-state structures of [N(PPh₃)₂]₂[FeIr₄(CO)₁₅] and [PPh₄][Fe₂Ir₃(CO)₁₄]

Electronic Stabilization of Trigonal Bipyramidal Clusters: the Role of the Sn(II) Ions in [Pt₅(CO)₅{Cl₂Sn(μ-OR)SnCl₂}₃]^3– (R = H, Me, Et, ⁱPr)

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Bis(triphenylphosphine)iminium μ-hydrido-pentadecacarbonylpentaosmate, [(Ph3P)2N]+[HOs5(CO)15]−

Cited by 20 publications

References 3 publications

Chemical activation of pentaosmium carbonyl clusters: synthesis, structure, and reactivity of [Os5(CO)15(NCMe)] and [Os5H2(CO)14(NCMe)]; crystal structures of [Os5(CO)15{P(OMe)3}] and [Os5H2(CO)14(PEt3)]

Chemical activation of pentaosmium carbonyl clusters: synthesis, structure, and reactivity of [Os5(CO)15(NCMe)] and [Os5H2(CO)14(NCMe)]; crystal structures of [Os5(CO)15{P(OMe)3}] and [Os5H2(CO)14(PEt3)]

Synthesis and characterization of pentanuclear Fe–Ir carbonyl clusters. Solid-state structures of [N(PPh3)2]2[FeIr4(CO)15] and [PPh4][Fe2Ir3(CO)14]

Electronic Stabilization of Trigonal Bipyramidal Clusters: the Role of the Sn(II) Ions in [Pt5(CO)5{Cl2Sn(μ-OR)SnCl2}3]3– (R = H, Me, Et, iPr)

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Bis(triphenylphosphine)iminium μ-hydrido-pentadecacarbonylpentaosmate, [(Ph₃P)₂N]⁺[HOs₅(CO)₁₅]⁻

Synthesis and characterization of pentanuclear Fe–Ir carbonyl clusters. Solid-state structures of [N(PPh₃)₂]₂[FeIr₄(CO)₁₅] and [PPh₄][Fe₂Ir₃(CO)₁₄]

Electronic Stabilization of Trigonal Bipyramidal Clusters: the Role of the Sn(II) Ions in [Pt₅(CO)₅{Cl₂Sn(μ-OR)SnCl₂}₃]^3– (R = H, Me, Et, ⁱPr)