Addition of dimethylphenylphosphine to µ- and µ<sub>3</sub>-alkynyl and µ<sub>3</sub>- allenyl ligands in triosmium clusters: X-ray crystal structures of three zwitterionic adducts

Henrick, Kim; McPartlin, Mary; Deeming, Antony J.; Hasso, S.; Manning, Peter J.

doi:10.1039/dt9820000899

Cited by 45 publications

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“…The alkyne cluster Os3(CO)10(C2H2) gives the PMe2Ph adduct (6), O s3H (C O )9(CeeCR) gives 7, and Os3H(CO)9(C R = C = C H 2) gives 8. The X-ray structures of 6, 7 (R = H) and 8 (R = Me) have been determined (Henrick et al 1982). In contrast, other alkyne clusters of the type Os3(CO)10(alkyne) do not add PMe2Ph, other than by slow reaction to give substitution compounds.…”

Section: (D) Attack At Organic Ligandsmentioning

confidence: 99%

Nucleophilic addition at u ₃ -alkyne clusters leading to carbon-carbon bond formation

Deeming

Manning

1982

Phil. Trans. R. Soc. Lond. A

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Reactions of nucleophiles with triosmium carbonyl clusters, especially those containing unsaturated hydrocarbon ligands, are discussed. Attack may be at CO, the metal atoms, at carbon of the organic ligand, or, where there are acidic metal-bound hydrogen atoms, deprotonation to give anionic clusters may occur. New results on the reactions of LiBHEt3 with p3-alkyne clusters of type Os3(CO)10 (RC2R') are considered in the light of the range of possible sites of attack. Protonation of anionic species that are formed gives hydrogenation products with or without the loss of CO. Os3H2(CO)9(RC2R') is usually a minor product, while C-C coupling leads to Os3H(CO)9(CRCR'COH) (in general the major product) and to Os3H(CO)9- (CRCR'CH). With terminal alkynes RC2H H-atom transfer accompanies C-C coupling to give Os3H(CO)9(RC—C =C H 2) in substantial amounts. The initial site of hydride attack (CO, alkyne or metal) is considered in the context of low-temperature 1H n.m.r. results.

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Section: (D) Attack At Organic Ligandsmentioning

confidence: 99%

Nucleophilic addition at u ₃ -alkyne clusters leading to carbon-carbon bond formation

Deeming

Manning

1982

Phil. Trans. R. Soc. Lond. A

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“…In terms of bonding description, complex 1 can be considered to be zwitterionic in nature which creates an overall asymmetric charge distribution. Both spectroscopic (IR) and structural features suggest that the tertiary phosphine molecule adds at the µ3-carbon atom to give an zwitterionic complex containing a phosphonium centre and a negative charge on the cluster framework ( Scheme 2 ) [ 19 , 22 ]. To count the cluster valence electrons, complex 1 is a 47 electron system which can provide evidence for the electron-withdrawing nature of the Os 3 C core.…”

Section: Resultsmentioning

confidence: 99%

Synthesis and Crystal Structure of a New Triosmium Alkylidyne Carbonyl Cluster Containing a Chiral Ferrocenylphosphine Ligand

Wong

2005

Molecules

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The synthesis, spectroscopic characterization and X-ray crystal structure of a new chiral triosmium alkylidyne carbonyl cluster, (R,S)-[Os3(μ-H)2(CO)9{μ3-CPPh2(η5-C5H4)Fe(η5-C5H3(PPh2)CH(Me)NMe2)}] (1) are described. Compound 1 crystallizes in the non-centrosymmetric space group P21 and its absolute configuration has been established. The structure consists of an Os3C metal core with one of the PPh2 moieties of the chiral ferrocenylphosphine bonded to the apical alkylidyne carbon atom to give a zwitterionic cluster complex, reminiscent of the phosphorus ylide.

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“…This type of reaction is found in the reaction of [Ru 3 (m 3 -C 2 H 2 )(m-CO)(CO) 9 ] with dppm, which proceeds by nucleophilic attack of the P-atom at an electron-deficient C-atom of the coordinated ethyne and chelation of the second P-atom to the cluster. These reactions were first described many years ago in studies of reactions of monodentate tertiary phosphines with various alkyne ± ruthenium and alkyne ± osmium clusters [14].…”

Section: Methodsmentioning

confidence: 99%

Reactions of Ethyne with Some Ruthenium Cluster Complexes Containing dppm

Bruce

Pyke

Zaitseva

et al. 2001

HCA

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In memoriam Luigi M. Venanzi, who was an early mentor of the senior author and who first aroused his interest in organometallic chemistryReactions of ethyne with [Ru 3 (m-dppm)(CO) 10 ] have given isomeric complexes [Ru 3 (m 3 -C 6 H 6 )(CO) 6 (dppm)], one of which, 2, contains the dppm chelating an Ru-atom, together with a hexatrienetriyl ligand attached to the Ru 3 cluster to form a methylideneruthenacyclohexadiene system. The second isomer 3 contains the dppm bridging an RuÀRu bond, with the C 6 H 6 ligand forming a vinylruthenacyclopentadiene system. Also isolated was the open-chain Ru 3 complex 4 containing a ruthenacyclopentadiene attached to the central Ru-atom; the other RuÀRu vector is bridged by a PPh 2 CHPPh 2 C 4 H 5 ligand, formed by a novel insertion of two ethyne molecules into an RuÀP bond. The reaction of ethyne with [Ru 3 (m-H)(m 3 -C 2 H 2 )(CO) 9 ] proceeded by attack at the coordinated alkyne and at the cluster to give a cluster-bonded PPh 2 CH 2 PPh 2 CCH system in 7. Thermolysis of [Ru 3 (m-H)(m 3 -C 2 SiMe 3 )(m-dppm)(CO) 7 ] (8; refluxing MeOH) in the presence of KF gave [Ru 6 (m-CCH 2 ) 2 (m-dppm) 2 (CO) 12 ] (9; 80%); similar reactions carried out with [RuClCp(PPh 3 ) 2 ] also present gave 9 (67%) together with [Ru 3 (m-H)(m 3 -C 2 H)(m-dppm)(CO) 6 (PPh 3 )] (11; 23%). The molecular structures of 2, 3, 4, 7, 9, and 11, some as differently solvated forms, have been determined by single-crystal Xray studies.Helvetica Chimica Acta ± Vol. 84 (2001) 3197 treating [RuClCp(PPh 3 ) 2 ] with a variety of trimethylsilylated alkynes and poly-ynes in the presence of KF in MeOH [7]. It is likely that this reaction proceeds with intermediate formation of the corresponding vinylidene, which is deprotonated by the fluoride (or methoxide) base. We were interested to determine whether similar reactions might be applied to cluster-bonded silylated alkynes or alkynyls. This paper also describes the protodesilylation reaction of [Ru 3 (m-H)(m 3 -C 2 SiMe 3 )(mdppm)(CO) 7 ] [5b], from which an unusual hexanuclear cluster containing vinylidene ligands was isolated.Results and Discussion. ± Reactions of Ethyne with [Ru 3 (m-dppm)(CO) 10 ] (1). Reactions between [Ru 3 (m-dppm)(CO) 10 ] (1) and ethyne were carried out by passing a stream of the gas through a solution of the complex, monitoring the reaction periodically by TLC. The same products were formed either on heating, or from a reaction carried out at room temperature in the presence of Me 3 NO. Thus, from a reaction carried out in refluxing THF for 2 h, four complexes were separated by preparative TLC (Scheme 1). Elemental analyses and mass spectrometry enabled empirical compositions to be established, while single-crystal X-ray studies were required to determine the precise molecular structures of several of the complexes.

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Addition of dimethylphenylphosphine to µ- and µ₃-alkynyl and µ₃- allenyl ligands in triosmium clusters: X-ray crystal structures of three zwitterionic adducts

Cited by 45 publications

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Nucleophilic addition at u ₃ -alkyne clusters leading to carbon-carbon bond formation

Nucleophilic addition at u ₃ -alkyne clusters leading to carbon-carbon bond formation

Synthesis and Crystal Structure of a New Triosmium Alkylidyne Carbonyl Cluster Containing a Chiral Ferrocenylphosphine Ligand

Reactions of Ethyne with Some Ruthenium Cluster Complexes Containing dppm

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Addition of dimethylphenylphosphine to µ- and µ3-alkynyl and µ3- allenyl ligands in triosmium clusters: X-ray crystal structures of three zwitterionic adducts

Cited by 45 publications

References 0 publications

Nucleophilic addition at u 3 -alkyne clusters leading to carbon-carbon bond formation

Nucleophilic addition at u 3 -alkyne clusters leading to carbon-carbon bond formation

Synthesis and Crystal Structure of a New Triosmium Alkylidyne Carbonyl Cluster Containing a Chiral Ferrocenylphosphine Ligand

Reactions of Ethyne with Some Ruthenium Cluster Complexes Containing dppm

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Addition of dimethylphenylphosphine to µ- and µ₃-alkynyl and µ₃- allenyl ligands in triosmium clusters: X-ray crystal structures of three zwitterionic adducts

Nucleophilic addition at u ₃ -alkyne clusters leading to carbon-carbon bond formation

Nucleophilic addition at u ₃ -alkyne clusters leading to carbon-carbon bond formation