Phosphane‐Substituted Selenido−(carbonyl)iron and −(carbonyl)ruthenium Clusters: Structures, Fluxionality and Reactivity

Graiff, Claudia; Predieri, Giovanni; Tiripicchio, António

doi:10.1002/ejic.200200661

Cited by 18 publications

(4 citation statements)

References 39 publications

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“…These structural motifs extend the knowledge of carbonylruthenium chalcogenide clusters 42. The structure of the 74‐electron anion [ 15 ] − may be described by a slightly distorted Ru 5 square pyramid spanned by a μ 4 ‐Te ligand.…”

Section: Introductionsupporting

confidence: 52%

Metal Telluride Clusters — From Small Molecules to Polyhedral Structures

Wächter

2004

Eur J Inorg Chem

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Section: Introductionsupporting

confidence: 52%

Metal Telluride Clusters — From Small Molecules to Polyhedral Structures

Wächter

2004

Eur J Inorg Chem

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“…The first yellow band (Rf = 0.81) gave the new compound 3 J H,H = 6.6 Hz, 4 J H,P = 3.0 Hz, 4 Thermal treatment at 80 • C of cluster 2; conversion to cluster 7. A solution of cluster 2 (0.154 g, 0.15 mmol) in toluene (20 mL) was heated at 80 • C for 1 h. Conversion to cluster 7 was detected by 1 H NMR, 31 P{ 1 H} NMR, FTIR (Yield 82% by NMR peak integration).…”

Section: Pyrolitic Reaction Between Hetsns and [Ru 3 (Co)mentioning

confidence: 99%

Reactivity of the zwitterionic ligand EtNHC(S)Ph₂PNPPh₂C(S)NEt towards [Ru₃(CO)₁₂]. Sulfur transfer and ligand fragmentation leading to the methideylamide [-N(Et)-CH(R)-] μ₃-bridging moiety

et al. 2009

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The reaction of EtNHC(S)Ph2P[double bond, length as m-dash]NP+Ph2C(S)N(-)Et (HEtSNS) with [Ru3(CO)12] has been carried out under two different experimental conditions: in the first case [Ru3(CO)12], previously turned into the labile intermediate [Ru3(CO)10(CH3CN)2], afforded, at room temperature in dichloromethane, the trinuclear clusters [Ru3(CO)11(CNEt)] (1), [Ru3(CO)9(micro-H)[(micro-S:kappa-P)Ph2PN[double bond, length as m-dash]PPh2C(S)NEt]] (2), [Ru3(CO)9(micro-H)[(micro-S:kappa-P)Ph2PN[double bond, length as m-dash]P(S)Ph2]] (3) and [Ru3(CO)10[(micro-kappa2P)Ph2PNHPPh2]] (3). Ligand fragmentation occurs via loss of EtNC or EtNCS, without sulfur transfer to the cluster core. In the second case, [Ru3(CO)12] reacted with HEtSNS in toluene at 70 degrees C, giving the trinuclear clusters , [Ru3(CO)7(CNEt)(micro3-S)[(micro2-N:eta1-C:kappa1-P)Ph2PN[double bond, length as m-dash]PPh2C(H)NEt]] (6), [Ru3(CO)8)(micro3-S)[(micro2-N:eta-C:kappa-P)Ph2PN[double bond, length as m-dash]PPh2C(H)NEt]] (6) and [Ru3(CO)6(micro3-CO)(micro3-S)(EtNC)[(micro-kappa2P) Ph2PNHPPh2]] (7). The last three compounds derive from ligand fragmentation and sulfur transfer to the metal cluster. All compounds were characterized by spectroscopy (NMR, IR) and the molecular structures of , and were determined by single-crystal X-ray diffraction. Cluster preserves the original Ru3 triangular core in which an edge is bridged by a hydride ligand and by the sulfur atom of the Ph2PN[double bond, length as m-dash]PPh2C(S)NEt ligand. Cluster shows an open triangle of Ru atoms capped by a micro3-sulfide and by the unprecedented methideylamide -N(Et)CH(R)-micro3-bridging moiety of the Ph2PN[double bond, length as m-dash]PPh2C(H)NEt ligand. It formally derives from cluster by substitution of ethyl isonitrile with one CO molecule. Finally, cluster displays a Ru3(micro3-S)(micro3-CO) trigonal bipyramidal core.

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“…However, the only known compounds in the gas phase when the substituent is a halogen atom, again in parallel to the sulfur analogues, − are those in which the halogen is attached to the Se atom, , whereas those in which the halogen is attached to the N atom are not experimentally known. These findings and the fact that, although selenium derivatives have received significant attention in the past decade, − many questions on their chemistry and bonding are still open, prompted us to undergo a study on the bonding and relative stabilities of substituted selenocyanates and isoselenocyanates, when the substituent is a methyl group, as the simplest case of alkyl group, and when the substituent is F, Cl, and Br.…”

Section: Introductionmentioning

confidence: 99%

On the Bonding of Selenocyanates and Isoselenocyanates and Their Protonated Derivatives

Trujillo

Mó

Yáñez

et al. 2008

J. Chem. Theory Comput.

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The structure, bonding, and protonation of NCSeX and XNCSe (X = Me, F, Cl, Br) derivatives has been investigated at the B3LYP/6-311++G(3df,2p)//B3LYP/6-31+G(d,p) level of theory. Three different approaches, namely, ELF, AIM, and NBO indicate that three main factors are responsible for the enhanced stability of the selenocyanates with respect to the isoselenocyanates when the substituents are halogens, whereas for alkyl substituents, it is the other way around: (a) the Se-X (X = F, Cl, Br) bonds are much stronger than the Se-X (X = Me); (b) the N-X (X = F, Cl, Br) bonds are much weaker than the N-X (X = Me) ones; (c) on going from the selenocyanates to the isoselenocyanates, when the substituents are halogen atoms, there is a significant weakening of the CN bond, which becomes essentially a double bond, whereas upon methyl substitution the CN bond retains its triple bond character. The same stability trends are observed for the corresponding N-protonated species. More importantly, the calculated stability differences are rather similar to those obtained for the neutral compounds, so that selenocyanates and isoselenocyanates exhibit rather similar basicities in the gas phase. Both types of isomers behave as gas-phase nitrogen bases.

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Phosphane‐Substituted Selenido−(carbonyl)iron and −(carbonyl)ruthenium Clusters: Structures, Fluxionality and Reactivity

Abstract: For Abstract see ChemInform Abstract in Full Text.

Cited by 18 publications

References 39 publications

Metal Telluride Clusters — From Small Molecules to Polyhedral Structures

Metal Telluride Clusters — From Small Molecules to Polyhedral Structures

Reactivity of the zwitterionic ligand EtNHC(S)Ph₂PNPPh₂C(S)NEt towards [Ru₃(CO)₁₂]. Sulfur transfer and ligand fragmentation leading to the methideylamide [-N(Et)-CH(R)-] μ₃-bridging moiety

On the Bonding of Selenocyanates and Isoselenocyanates and Their Protonated Derivatives

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Phosphane‐Substituted Selenido−(carbonyl)iron and −(carbonyl)ruthenium Clusters: Structures, Fluxionality and Reactivity

Abstract: For Abstract see ChemInform Abstract in Full Text.

Cited by 18 publications

References 39 publications

Metal Telluride Clusters — From Small Molecules to Polyhedral Structures

Metal Telluride Clusters — From Small Molecules to Polyhedral Structures

Reactivity of the zwitterionic ligand EtNHC(S)Ph2PNPPh2C(S)NEt towards [Ru3(CO)12]. Sulfur transfer and ligand fragmentation leading to the methideylamide [-N(Et)-CH(R)-] μ3-bridging moiety

On the Bonding of Selenocyanates and Isoselenocyanates and Their Protonated Derivatives

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Reactivity of the zwitterionic ligand EtNHC(S)Ph₂PNPPh₂C(S)NEt towards [Ru₃(CO)₁₂]. Sulfur transfer and ligand fragmentation leading to the methideylamide [-N(Et)-CH(R)-] μ₃-bridging moiety