Transformation of an isocyanide ligand in the coordination sphere of an osmium cluster. Reactions of osmium isocyanide complexes with amines

Lin, Yen Wen; Gau, Han Mou; Wen, Yuh Sheng; Lu, Kuang Lieh

doi:10.1021/om00040a008

Cited by 20 publications

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“…Compound 2a can be alternatively prepared in a better yield (76%) from the reaction of 1 with PhCH 2 NPPh 3 in chlorobenzene at room temperature. (Triphenylphosphino)alkylimine reagents are known to react with metal carbonyl complexes to yield metal isocyanide substituted compounds . On the other hand, irradiation of a chlorobenzene solution of 1 in the presence of an excess (30 equiv) of benzyl isocyanide by a medium-pressure Hg lamp for 3 days at room temperature gives the isocyanide-inserted product Os 3 (CO) 9 ( μ 3 -CNR)( μ 3 - η 1 : η 2 : η 1 -C 60 ) ( 2b ) in a low yield (11%).…”

Section: Resultsmentioning

confidence: 99%

Ligand-Induced Conversion of π to σ C₆₀−Metal Cluster Complexes: Full Characterization of the μ₃-η¹:η²:η¹-C₆₀ Bonding Mode

Song

Lee

et al. 2002

Organometallics

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The reaction of Os3(CO)9(μ 3-η 2:η 2:η 2-C60) (1) with PhCH2NPPh3 in chlorobenzene affords the benzyl isocyanide substituted product Os3(CO)8(CNR)(μ 3-η 2:η 2:η 2-C60) (2a, R = CH2Ph) in 76% yield. Photolysis of 1 in the presence of an excess of benzyl isocyanide gives the isocyanide-inserted product Os3(CO)9(μ 3-CNR)(μ 3-η 1:η 2:η 1-C60) (2b) in 11% yield. Thermal reaction of 2a with an excess of RNC in chlorobenzene at 80 °C produces two isocyanide-inserted, isomeric products, Os3(CO)8(CNR)(μ 3-CNR)(μ 3-η 1:η 2:η 1-C60) (3a, 22%; 3b, 27%). The two isomers 3a and 3b can be selectively prepared by photolysis of 2a in the presence of excess isocyanide in 49% yield and by decarbonylation of 2b with Me3NO/MeCN and subsequent reaction with isocyanide in 56% yield, respectively. Compounds 2a,b and 3a,b have been characterized by microanalytical and spectroscopic methods. In particular, the sp3 carbons of M−C(C60) σ-interactions in μ 3-η 1:η 2:η 1-C60 complexes exhibit unique upfield resonances around 39 ppm in the 13C NMR spectra, compared to the π-bonded sp3 carbon resonances observed in the range of 95−65 ppm. The X-ray crystallographic studies for 2a,b and 3a,b reveal that μ 3-η 2:η 2:η 2-C60 ligands in 1 and 2a transform into new σ-type μ 3-η 1:η 2:η 1-C60 ligands in 2b and 3a,b by insertion of the isocyanide ligand concomitant with Os−Os bond cleavage, forming a bent triosmium framework. In compounds 2b and 3b, a boat-shaped 1,4-cyclohexadiene-like C6 ring in the C60 molecule is clearly observed and the M−C60 σ-bond distances (average 2.24 Å) are shorter than the π-bond lengths (average 2.41 Å). This study represents a novel ligand-induced conversion of π to σ C60−metal complexes.

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Section: Resultsmentioning

confidence: 99%

Ligand-Induced Conversion of π to σ C₆₀−Metal Cluster Complexes: Full Characterization of the μ₃-η¹:η²:η¹-C₆₀ Bonding Mode

Song

Lee

et al. 2002

Organometallics

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“…[6] The iron isocyanide complex 4 has been synthesised by reaction of pentacarbonyliron(o) with a phosphinimine. [7] This reaction has occasionally been exploited in a similar manner, [8] (see below) although it is of note that phosphinimines are frequently moisture-and/or air-sensitive. [9] The challenges associated with the present approaches to isocyanide ligand synthesis have led to the vast majority of isocyanide ligands reported to date having very simple structures.…”

Section: Introductionmentioning

confidence: 99%

Phosphoramidate-Mediated Conversion of Carbonyl Ligands into Isocyanide Ligands: A New Approach to Chiral Isocyanide Ligands

et al. 2002

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Metal isocyanides have been used and studied by organometallic chemists for many years and, as a result, they have a rich and interesting chemistry. The nature of metal-free isocyanides and the methods of making isocyanide complexes, however, has resulted in the vast majority of studies to date being performed with structurally simple isocyanides. We report here a new approach to the synthesis of isocyanide ligands that involves the reaction of a metal carbonyl ligand with the anion of a phosphoramidate. As phosphoramidates can be synthesised in one step from amines, our method means that the structural diversity of readily available amines, particularly chiral amines, can now be incorporated into isocyanide ligands.

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“…Compound 5 can be alternatively prepared from the reaction of 1 with excess Ph 3 PNCH 2 Ph at room temperature in 59% yield. Triphenylphosphinoalkylimine reagents are known to react with metal carbonyl complexes to yield metal isocyanide substituted compounds . Heating a chlorobenzene solution of 5 at 55 °C under 3 atm of carbon monoxide for 36 h produces the μ,η 2 :η 2 -C 60 complex 4 as the only isolable product (16%) with extensive decomposition, which is another demonstration of the reversible interconversion between μ,η 2 :η 2 -C 60 and μ 3 ,η 2 :η 2 :η 2 -C 60 by addition and loss of a carbonyl ligand.…”

Section: Resultsmentioning

confidence: 99%

Reversible Interconversion between μ,η²:η²- and μ₃,η²:η²:η²-C₆₀ on a Carbido Pentaosmium Cluster Framework

et al. 2001

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Decarbonylation of Os 5 (CO) 14 (PPh 3 ) by 2 equiv of Me 3 NO/CH 3 CN at room temperature followed by reaction with C 60 in refluxing chlorobenzene produces Os 5 C(CO) 11 (PPh 3 )(µ 3 ,η 2 : η 2 :η 2 -C 60 ) (1) in 44% yield. Thermal treatment of 1 at 80 °C under 1 atm of carbon monoxide affords Os 5 C(CO) 12 (PPh 3 )(µ,η 2 :η 2 -C 60 ) (2) in good yield (72%). Upon thermolysis of 2 at 132 °C, 2 is cleanly reconverted to 1 (73%) by loss of a carbonyl ligand. Reaction of 1 with benzyl isocyanide at room temperature gives the addition product Os 5 C(CO) 11 (CNCH 2 C 6 H 5 )(PPh 3 )-(µ 3 ,η 2 :η 2 :η 2 -C 60 ) (3) in 85% yield. Thermolysis of 3 at 100 °C forms the isomeric Os 5 C(CO) 11 -(CNCH 2 C 6 H 5 )(PPh 3 )(µ,η 2 :η 2 -C 60 ) (4) in 64% yield. Treatment of 4 with 1 equiv of Me 3 NO/ CH 3 CN at room temperature followed by heating at 132 °C in chlorobenzene gives Os 5 C(CO) 10 (CNCH 2 C 6 H 5 )(PPh 3 )(µ 3 ,η 2 :η 2 :η 2 -C 60 ) (5) in 71% yield. Compound 5 can be alternatively prepared from the reaction of 1 with excess Ph 3 PdNCH 2 Ph at room temperature in 59% yield. Heating a chlorobenzene solution of 5 at 55 °C under 3 atm of carbon monoxide produces 4 as the only major product (16%). Treatment of Ru 5 C(CO) 11 (PPh 3 )(µ 3 ,η 2 :η 2 :η 2 -C 60 ) (1′) with benzyl isocyanide at room temperature forms Ru 5 C(CO) 11 (CNCH 2 C 6 H 5 )(PPh 3 )(µ 3 ,η 2 : η 2 :η 2 -C 60 ) (3′) in 90% yield. Reaction of 1′ with benzyl isocyanide at a slightly elevated temperature of 40 °C affords Ru 5 C(CO) 10 (CNCH 2 C 6 H 5 )(PPh 3 )(µ 3 ,η 2 :η 2 :η 2 -C 60 ) (5′) in an almost quantitative yield of 96%. Compounds 1-5, 3′, and 5′, isolated as crystalline solids, have been characterized by microanalytical and spectroscopic methods. Molecular structures of 1-4 and 5′ have been elucidated by X-ray crystallographic studies.

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Transformation of an isocyanide ligand in the coordination sphere of an osmium cluster. Reactions of osmium isocyanide complexes with amines

Cited by 20 publications

References 0 publications

Ligand-Induced Conversion of π to σ C₆₀−Metal Cluster Complexes: Full Characterization of the μ₃-η¹:η²:η¹-C₆₀ Bonding Mode

Ligand-Induced Conversion of π to σ C₆₀−Metal Cluster Complexes: Full Characterization of the μ₃-η¹:η²:η¹-C₆₀ Bonding Mode

Phosphoramidate-Mediated Conversion of Carbonyl Ligands into Isocyanide Ligands: A New Approach to Chiral Isocyanide Ligands

Reversible Interconversion between μ,η²:η²- and μ₃,η²:η²:η²-C₆₀ on a Carbido Pentaosmium Cluster Framework

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Transformation of an isocyanide ligand in the coordination sphere of an osmium cluster. Reactions of osmium isocyanide complexes with amines

Cited by 20 publications

References 0 publications

Ligand-Induced Conversion of π to σ C60−Metal Cluster Complexes: Full Characterization of the μ3-η1:η2:η1-C60 Bonding Mode

Ligand-Induced Conversion of π to σ C60−Metal Cluster Complexes: Full Characterization of the μ3-η1:η2:η1-C60 Bonding Mode

Phosphoramidate-Mediated Conversion of Carbonyl Ligands into Isocyanide Ligands: A New Approach to Chiral Isocyanide Ligands

Reversible Interconversion between μ,η2:η2- and μ3,η2:η2:η2-C60 on a Carbido Pentaosmium Cluster Framework

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Ligand-Induced Conversion of π to σ C₆₀−Metal Cluster Complexes: Full Characterization of the μ₃-η¹:η²:η¹-C₆₀ Bonding Mode

Ligand-Induced Conversion of π to σ C₆₀−Metal Cluster Complexes: Full Characterization of the μ₃-η¹:η²:η¹-C₆₀ Bonding Mode

Reversible Interconversion between μ,η²:η²- and μ₃,η²:η²:η²-C₆₀ on a Carbido Pentaosmium Cluster Framework