A comparison of the rates of intramolecular hydrogen migration in the molecules [Mo(η-C7H8)2]n+to give [Mo(η-C7H7)(η-C7H9)]n+, n= 0 or 1: crystal structures of [Mo(η-C7H8)2], [Mo(η-C7H7)(η-C7H9)], and [Mo(η-C7H8)2][BF4]
“…At elevated temperatures (about 100 °C) the η 4 - and η 6 -ligands in 1 − 3 undergo hydrogen migrations. It was shown for both types of complexes that only the endo hydrogens of the methylene groups are involved in this process. 1d,5a,b …”
Section: Discussionmentioning
confidence: 99%
“…For example, abstraction of hydride is a common reaction with [CpCo(η 4 -C 5 H 6 )] ( 1 ) and [(CO) 3 M(η 6 -C 7 H 8 ]] [ 2 (M = Cr), 3 (M = Mo), 4 (M = W)]. , Some activated alkynes 1d, and even styrene stereospecifically insert into a methylene CH bond of 1a to give exo -substituted derivatives. Intra- and interligand hydride shifts have been observed both in η 4 -cyclopentadiene 1d and η 6 -cycloheptatriene complexes . It appears that migration of the endo methylene hydrogen takes place during these rearrangements. 1d,5a …”
Section: Introductionmentioning
confidence: 99%
“…Intra- and interligand hydride shifts have been observed both in η 4 -cyclopentadiene 1d and η 6 -cycloheptatriene complexes . It appears that migration of the endo methylene hydrogen takes place during these rearrangements. 1d,5a …”
The heterodinuclear complexes [(CO) 3 M(µ-H)(µ-C 7 H 7 )Co(η-C 5 Me. The X-ray crystal structures of 7 and 8 have been determined. The boat-shaped bridging cycloheptatrienyl ligands adopt the η 4 (M):η 3 (Co) coordination in the crystalline state. The rather long M-Co vectors were found to be bridged by hydrido ligands, making up 3c-2e MHCo bonds. In solution, hindered rotation of the C 7 H 7 ring was observed, which, in the case of 7, could be frozen on the NMR time scale at 200 K.
ResultsSyntheses. When equimolar petroleum ether solutions of 2 and the Jonas reagent 5a were allowed to
“…At elevated temperatures (about 100 °C) the η 4 - and η 6 -ligands in 1 − 3 undergo hydrogen migrations. It was shown for both types of complexes that only the endo hydrogens of the methylene groups are involved in this process. 1d,5a,b …”
Section: Discussionmentioning
confidence: 99%
“…For example, abstraction of hydride is a common reaction with [CpCo(η 4 -C 5 H 6 )] ( 1 ) and [(CO) 3 M(η 6 -C 7 H 8 ]] [ 2 (M = Cr), 3 (M = Mo), 4 (M = W)]. , Some activated alkynes 1d, and even styrene stereospecifically insert into a methylene CH bond of 1a to give exo -substituted derivatives. Intra- and interligand hydride shifts have been observed both in η 4 -cyclopentadiene 1d and η 6 -cycloheptatriene complexes . It appears that migration of the endo methylene hydrogen takes place during these rearrangements. 1d,5a …”
Section: Introductionmentioning
confidence: 99%
“…Intra- and interligand hydride shifts have been observed both in η 4 -cyclopentadiene 1d and η 6 -cycloheptatriene complexes . It appears that migration of the endo methylene hydrogen takes place during these rearrangements. 1d,5a …”
The heterodinuclear complexes [(CO) 3 M(µ-H)(µ-C 7 H 7 )Co(η-C 5 Me. The X-ray crystal structures of 7 and 8 have been determined. The boat-shaped bridging cycloheptatrienyl ligands adopt the η 4 (M):η 3 (Co) coordination in the crystalline state. The rather long M-Co vectors were found to be bridged by hydrido ligands, making up 3c-2e MHCo bonds. In solution, hindered rotation of the C 7 H 7 ring was observed, which, in the case of 7, could be frozen on the NMR time scale at 200 K.
ResultsSyntheses. When equimolar petroleum ether solutions of 2 and the Jonas reagent 5a were allowed to
“…Cyclic voltammetric investigations on the mixed-sandwich cycloheptatrienyl systems (η-cycloheptatrienyl)(η-cyclopentadienyl)metal (M = Cr, 6 Mo 10 or W 12 ) and (η-cycloheptadienyl)(η-cycloheptatrienyl)molybdenum 25 reveal reversible one-electron oxidations to the corresponding 17-electron radical cations which in selected cases have been isolated and fully characterised. By contrast, investigations on the redox chemistry of (η-arene…”
Section: Electrochemical Investigations and Synthetic Redox Chemistrymentioning
confidence: 99%
“…Structural studies have been reported for each of the main classes of mixed sandwich cycloheptatrienyl systems, (η-cycloheptatrienyl)(η-cyclopentadienyl)metal, 10 (η-cycloheptadienyl)-(η-cycloheptatrienyl)metal 25 and [M(η-arene)(η-C 7 H 7 )] ϩ , 26 but in all three cases the complex selected for investigation was one of molybdenum; although limited structural data are also available for [Cr(η-C 5 H 5 )(η-C 7 H 7 )] 8 these are not substantiated by a full report. A summary of the principal aspects of the structural data available for the representative cycloheptatrienyl sandwich systems is presented in Table 6 and three points of interest arise.…”
A heterometallic MÀ M' bond formation is a key to construct atomically precise bimetallic clusters and materials. However, it is sometimes not straightforward to construct a heterometallic MÀ M' bond through conventional methods including redox condensation. Here, we found that a sandwich framework of π-conjugated unsaturated hydrocarbon ligands provides a unique coordination environment that facilitates unusual coupling of d 8 Rh I and d 10 M 0 (M = Pd, Pt). The molecular orbital analysis showed that the electron-accepting ability of the sandwich framework through back-donation allows the formation of a dσtype RhÀ Pd bond in a (d-d) 18 electron system.
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