Synthesis and reactivity of rhenium(I) tris(acetylene) complexes ReX(RC.tplbond.CR)3

Manion, A. B.; Erikson, Torsten K. G.; Spaltenstein, Esther; Mayer, James M.

doi:10.1021/om00110a007

Cited by 13 publications

(7 citation statements)

References 2 publications

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“…Resonances for 3-hexyne added to a solution of 3 remain sharp at these temperatures, so ligand exchange is not responsible for the coalescence. The fluxional process is most likely rotation of the alkyne ligand(s), as suggested for similar ReX(RC⋮CR) 3 , and W(L)(RC⋮CR) 3 compounds . The coalescence temperature is found to be 295 K for the methylene protons, indicating that Δ G ⧧ rotation = 14.0 ± 0.2 kcal/mol.…”

Section: Resultsmentioning

confidence: 65%

Hydroxide-, Amide-, and Sulfhydrylrhenium(I) Tris(alkyne) Complexes. Rearrangements to Rhenium(III) Bis(alkyne) Oxo and Nitrido Compounds¹

1997

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The rhenium hydroxide and amide complexes Re(OH)(EtC⋮CEt)3 (3) and Re(NH2)(EtC⋮CEt)3 (10) have been prepared by reaction of the related aquo and ammine complexes with KOH and NaNH2, respectively. The sulfhydryl compound Re(SH)(EtC⋮CEt)3 (13) is formed from Re(OSO2CF3)(EtC⋮CEt)3 and NaSH. Compound 3 spontaneously rearranges to the oxo−hydride complex Re(O)H(EtC⋮CEt)2 (4), and EtC⋮CEt in a first-order process (k = (5.6 ± 1.2) × 10-6 s-1 at 294 K). There is a primary isotope effect (k OH/k OD = 5 ± 1), and the rearrangement is unaffected by the presence of 1 M 3-hexyne. These data rule out a mechanism involving initial ligand loss followed by rearrangement. Instead, hydrogen migration from oxygen to rhenium occurs in the coordinatively saturated tris(alkyne) species 3, either synchronously with or prior to the loss of alkyne. Rearrangement is catalyzed by potassium alkoxides, apparently via deprotonation of 3 and concomitant loss of EtC⋮CEt to the oxo anion (EtC⋮CEt)2ReO- (5), which is reprotonated by ROH. Surprisingly, isolated samples of 5 are not catalysts, apparently due to its slow proton transfer reactions. The amide complex 10 rearranges to the unusual μ-nitrido complex (EtC⋮CEt)3Re−N⋮Re(H)(EtC⋮CEt)2 (11), which has been characterized spectroscopically. This reaction is similar to that of the hydroxide 3 in that a hydrogen moves from N or O to the rhenium center, with oxidation of the metal. The mechanism of rearrangement is quite different, however, as added alkynes strongly inhibit conversion of 10 to 11, indicating initial 3-hexyne dissociation from 10. No rearrangement has been observed for the sulfhydryl compound 13, which decomposes at 150 °C.

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Section: Resultsmentioning

confidence: 65%

Hydroxide-, Amide-, and Sulfhydrylrhenium(I) Tris(alkyne) Complexes. Rearrangements to Rhenium(III) Bis(alkyne) Oxo and Nitrido Compounds¹

1997

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“…Tetra-coordinated alkyne complexes are known for neighboring elements, e.g., for W(0) (e.g., [W(CO)(η 2 -PhCCPh) 3 ]). , Examples with Re are more scarce. They are accessible from [ReX(η 2 -RCCR) 3 ] (X = I and OSiMe 3 ; R = Me and Et), obtained from a two-step procedure with [ReO(I) 3 (PPh 3 ) 2 ]. , 1 H NMR analysis depicts two sets of signals of equal intensities for the PhCCPh ligands in [ 14 ] + . Thus, the three PhCCPh ligands are chemically equivalent, but in each of them, the phenyl moieties are in different chemical environments.…”

Section: Resultsmentioning

confidence: 99%

Exploring Rhenium Arene Piano-Stool Chemistry with [Re(η⁶-C₆H₆)(NCCH₃)₃]⁺: A Powerful Semi-Solvated Precursor

et al. 2023

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Thermal treatment of the ReIII hydride complex [ReH(η5-C6H7)(η6-C6H6)]+ in CH3CN results in the formation of [Re(η6-C6H6)(NCCH3)3]+. This semi-solvated complex is remarkably stable under an ambient atmosphere and exhibits a fast CH3CN self-exchange, which facilitates substitution reactions. The CH3CN ligands are replaced by σ-donating phosphines such as trimethyl phosphine (PMe3), triphenyl phosphine (PPh3), or the bidentate 1,2-bis(diphenylphosphino)ethane (dppe) to afford [Re(η6-C6H6)(NCCH3)3–x (PR3) x ]+ (if R = Me, then x = 2; if R = Ph, then x = 1 or 2) or [Re(η6-C6H6)(dppe)(NCCH3)]+, respectively. [Re(η6-C6H6)(NCCH3)3]+ also reacts with π-acceptors such as 2,2′-bipyridine (bipy), 1,10-phenanthroline (phen), or CO (1 atm) to give [Re(η6-C6H6)(L)(NCCH3)]+ (L = bipy or phen) and [Re(η6-C6H6)(CO)(NCCH3)2]+, respectively. The latter does not show any signs of decomposition after being exposed to an ambient atmosphere for multiple days. Additionally, [Re(η6-C6H6)(NCCH3)3]+ reacts with π-donors such as the dienes 2,3-dimethyl-1,3-butadiene (DMBD), norbornadiene (NBD), or 1,5-cyclooctadiene (COD) to give [Re(η6-C6H6)(η4-diene)(NCCH3)]+ (diene = DMBD, NBD, and COD). All three complexes are extremely stable and do not decompose during purification by preparative high-performance liquid chromatography (aqueous acidic gradient). In the presence of 18-crown-6, [Re(η6-C6H6)(NCCH3)3]+ reacts with lithium cyclopentadienyl to give the sandwich complex [Re(η5-C5H5)(η6-C6H6)]. Loss of the coordinated benzene was observed when treating [Re(η6-C6H6)(NCCH3)3]+ with diphenylacetylene (PhCCPh), yielding the tetra-coordinated [Re(NCCH3)(η2-PhCCPh)3]+.

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“…Manipulations were performed under an atmosphere of N 2 purified by passage through BTS catalyst (BASF) and molecular sieves (3 Å), using either standard Schlenk techniques or an inert atmosphere box. Re(O)(I) 3 (PPh 3 ) 2 , [Re(O) 2 (cyclam)](ClO 4 ), Re(O)(I)(MeC⋮CMe) 2 , Re(O)(Et)(MeC⋮CMe) 2 , Re(O)(Me)(MeC⋮CMe) 2 , Et 3 SiB(C 6 F 5 ) 4 , and (C 6 Me 3 H 4 )B(C 6 F 5 ) 4 29 were prepared according to published procedures. C 6 H 6 , C 6 D 6 , and THF were distilled from Na/Ph 2 CO; hexanes and pentane were distilled from Na/Ph 2 CO in the presence of tetraglyme; toluene was distilled from Na.…”

Section: Methodsmentioning

confidence: 99%

Rhenium Oxo Complexes of a Chelating Diyne Ligand. Synthesis and Study of the Kinetics of Protonation

Han

Stoessel

et al. 2001

Inorg. Chem.

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A series of oxo complexes, Re(O)X(diyne) (X = I, Me, Et), have been prepared from 2,7-nonadiyne and Re(O)I(3)(PPh(3))(2). Addition of B(C(6)F(5))(3) to Re(O)I(2,7-nonadiyne) (5) results in coordination of the oxo ligand to the boron. The protonation of Re(O)(X)(2-butyne)(2) and Re(O)(X)(2,7-nonadiyne)(2) with a variety of acids has been examined. With 5 and HBF(4)/Et(2)O, the ultimate product was [Re(CH(3)CN)(3)(I)(2,7-nonadiyne)](2+) (7). The conversion of 5 to 7 changes the conformation of the diyne ligand from a "chair" to a "boat" and shifts its propargylic protons considerably downfield in the (1)H NMR. The kinetics of the protonation of Re(O)I(2,7-nonadiyne) (5) by CF(3)SO(3)H in CH(3)CN have been monitored by visible spectroscopy, in a stopped-flow apparatus, and by low temperature (1)H NMR. Two second-order rate constants, presumably successive protonations, were observed in the stopped-flow, k(1) = 11.9 M(-)(1) s(-)(1) and k(2) = 3.8 M(-)(1) s(-)(1). Low temperature (1)H NMR spectroscopy indicated that the resulting solution contained a mixture of two doubly protonated intermediates X and Y, each of which slowly formed the product 7 via an acid-independent process.

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Synthesis and reactivity of rhenium(I) tris(acetylene) complexes ReX(RC.tplbond.CR)3

Cited by 13 publications

References 2 publications

Hydroxide-, Amide-, and Sulfhydrylrhenium(I) Tris(alkyne) Complexes. Rearrangements to Rhenium(III) Bis(alkyne) Oxo and Nitrido Compounds¹

Hydroxide-, Amide-, and Sulfhydrylrhenium(I) Tris(alkyne) Complexes. Rearrangements to Rhenium(III) Bis(alkyne) Oxo and Nitrido Compounds¹

Exploring Rhenium Arene Piano-Stool Chemistry with [Re(η⁶-C₆H₆)(NCCH₃)₃]⁺: A Powerful Semi-Solvated Precursor

Rhenium Oxo Complexes of a Chelating Diyne Ligand. Synthesis and Study of the Kinetics of Protonation

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Synthesis and reactivity of rhenium(I) tris(acetylene) complexes ReX(RC.tplbond.CR)3

Cited by 13 publications

References 2 publications

Hydroxide-, Amide-, and Sulfhydrylrhenium(I) Tris(alkyne) Complexes. Rearrangements to Rhenium(III) Bis(alkyne) Oxo and Nitrido Compounds1

Hydroxide-, Amide-, and Sulfhydrylrhenium(I) Tris(alkyne) Complexes. Rearrangements to Rhenium(III) Bis(alkyne) Oxo and Nitrido Compounds1

Exploring Rhenium Arene Piano-Stool Chemistry with [Re(η6-C6H6)(NCCH3)3]+: A Powerful Semi-Solvated Precursor

Rhenium Oxo Complexes of a Chelating Diyne Ligand. Synthesis and Study of the Kinetics of Protonation

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Hydroxide-, Amide-, and Sulfhydrylrhenium(I) Tris(alkyne) Complexes. Rearrangements to Rhenium(III) Bis(alkyne) Oxo and Nitrido Compounds¹

Hydroxide-, Amide-, and Sulfhydrylrhenium(I) Tris(alkyne) Complexes. Rearrangements to Rhenium(III) Bis(alkyne) Oxo and Nitrido Compounds¹

Exploring Rhenium Arene Piano-Stool Chemistry with [Re(η⁶-C₆H₆)(NCCH₃)₃]⁺: A Powerful Semi-Solvated Precursor