New directions in the chemistry of dirhodium(II) compounds

Cotton, F. Albert; Dunbar, Kim R.; Verbruggen, M.

doi:10.1021/ja00252a032

Cited by 57 publications

(26 citation statements)

References 0 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…After the preparation by Cotton et al in 1985 [1] of the first dirhodium(II) compound with formula cis-[Rh 2 A C H T U N G T R E N N U N G (C 6 H 4 PPh 2 ) 2 -A C H T U N G T R E N N U N G (CH 3 CO 2 H) 2 A C H T U N G T R E N N U N G (O 2 CCH 3 ) 2 ], which has two metalated phosphine ligands in a head-to-tail arrangement, other related compounds have been synthesized and structurally characterized. [2][3][4][5][6][7][8][9][10][11][12][13][14][15][16][17][18][19][20] Kinetic studies of the metalation reaction in such compounds have also been reported. [21][22][23] Dirhodium compounds containing two ortho-metalated aryl phosphine (PC) groups show high activity and chemoselectivity in the catalytic transformation of a-diazocarbonyl compounds, [24][25][26] and have been exploited for enantioselective reactions.…”

Section: Introductionmentioning

confidence: 99%

Dirhodium(II) Compounds with Bridging Thienylphosphines: Studies on Reversible P,C/P,S Coordination

Lloret‐Fillol

Estevan

Lahuerta

et al. 2009

Chemistry A European J

View full text Add to dashboard Cite

Monocyclometalated compound [Rh(2){(C(8)H(4)S)P(C(8)H(5)S)(2)}(CH(3)CO(2)H)(2)(O(2)CCH(3))(3)] (1 a) and bis-cyclometalated compound [Rh(2){(C(8)H(4)S)P(C(8)H(5)S)(2)}(2)(CH(3)CO(2)H)(2)(O(2)CCH(3))(2)] (2 a) have been isolated from the reaction of dirhodium tetraacetate and tris(2-benzo[b]thienyl)phosphine (2 BTP) using low acidic solutions. By contrast, in pure acetic acid the reaction of Rh(2)(O(2)CCH(3))(4) with 2 BTP and tris(2-thienyl)phosphine (2 TP), followed by replacement of the axial acetate ligands by chlorides, led to [Rh(2){(2-C(8)H(5)S)P(2-C(8)H(5)S)(2)}(2)Cl(2)(O(2)CCH(3))(2)] (3 b) and [Rh(2){(2-C(4)H(3)S)P(C(4)H(3)S)(2)}(2)Cl(2)(O(2)CCH(3))(2)] (5 b), respectively. These new dirhodium(II) compounds possess equatorial bridging ligands in a phosphorous-sulfur (P,S) coordination mode. The reversible switching between the P,C and P,S bonding mode of the phosphine has been studied in the monocyclometalated [Rh(2){(C(4)H(2)S)P(C(4)H(3)S)(2)}(CH(3)CO(2)H)(2)(O(2)CCH(3))(3)] (6 a), which was selectively transformed into compound [Rh(2){(2-C(4)H(3)S)P(C(4)H(3)S)(2)}(CF(3)SO(3))(CH(3)CO(2)H)(O(2)CCH(3))(3)] (7 c) in triflic acid media. Remarkably, compound 7 c reverts to the starting compound 6 a upon treatment with sodium acetate. Theoretical DFT calculations for both the P,C/P,S rearrangement and the base-promoted reversion have been performed to explain the experimental findings. Data suggest the P,C/P,S rearrangement occurs by means of a "concerted protonation-demetalation mechanism" followed by eta(2) coordination of the thienyl ring and subsequent isomerization to the S-eta(1)-coordination mode. In the reversion reaction, the base coordinated at the axial position would promote a concerted metalation-deprotonation mechanism.

show abstract

Section: Introductionmentioning

confidence: 99%

Dirhodium(II) Compounds with Bridging Thienylphosphines: Studies on Reversible P,C/P,S Coordination

Lloret‐Fillol

Estevan

Lahuerta

et al. 2009

Chemistry A European J

View full text Add to dashboard Cite

show abstract

“…In the presence of chloroform, it is reasonable to assume that dimeric rhodium species are formed with bridging chloride ligands. [25] For tetrahydroisoquinoline derivatives 14 and 15 it was also found that products of CH(sp 3 ) insertion were never detected. Different behaviour was observed with respect to compound 13, which indicated that the conformation of the piperidine ring was probably of fundamental importance to the reaction outcome.…”

Section: Discussionmentioning

confidence: 99%

Unusual Chemoselective Rh^II‐Catalysed Transformations of α‐Diazocarbonyl Piperidine Cores

Bonetti

Beccalli

Caselli

et al. 2014

Chemistry A European J

View full text Add to dashboard Cite

The reactivity of various α-diazocarbonyl piperidine scaffolds, characterised by an increased molecular complexity, was tested with various Rh(II) catalysts. The structure of the starting reagent is of relevance to the synthetic results. An unexpected dimerisation took place, starting from the simple piperidine scaffold, to give the hexahydrotetrazine ring system. Products derived from a nitrogen ylide intermediate or aromatic substitution (1,3,4,5-tetrahydro-2,5-methanobenzo[c]azepine and 1,2,3,3a-tetrahydrocyclopenta[de]isoquinolin-4(5 H)-one rings, respectively) were obtained from tetrahydroisoquinoline derivatives. The chemoselectivity of the reaction could be controlled by the choice of starting reagent, Rh(II) catalyst and the reaction conditions. Finally, it was found that the azepino heterocycle could coordinate to the catalyst to give new Rh(II) complexes.

show abstract

“…As for the cluster cation in 2[BAr [16] ). As far as we are aware, 3[BAr Density functional calculations on 2 2+ (symmetry unconstrained, PH 3 replaces PiPr 3 , S = 1/2) replicate closely the X-ray structure, with the hydride ligands bridging the spokes and canted towards the Rh 3 triangle to give S 6 symmetry ( Figure 3).…”

Section: Methodsmentioning

confidence: 99%

“…The closest structural analogues to 2[BAr 12 (thf) 6 } 2 ], [10] [Au 6 Ag(trip) 6 ] + (trip = triisopropylphenyl, [11] [Au 5 Fe 2 (CO) 8 (dppm) 2 ] + (dppm = bis(diphenylphosphino)methane), [12] [M 5 Fe 4 (CO) 16 ] 3À (M = Cu, Ag), [13] and [Os 6 (m-Hg)(m-PPh 2 ) 2 (CO) 20 ], [14] which have similar overall structures but no hydride ligands. The unusual structure of 2 2+ (and 3…”

mentioning

confidence: 99%

[Rh₇(PiPr₃)₆H₁₈][BAr^F₄]₂: A Molecular Rh(111) Surface Decorated with 18 Hydrogen Atoms

et al. 2007

View full text Add to dashboard Cite

Heptarhodium wagon wheel [Rh7(PiPr3)6H18][BArF4]2 (shown), which resembles a planar Rh(111) surface with 18 hydride ligands, was obtained together with [Rh8(PiPr3)6H16][BArF4]2 from the reaction of [Rh(PiPr3)2(nbd)][BArF4] and [Rh(nbd)2][BArF4] with hydrogen (ArF=C6H3(CF3)2, nbd=norbornadiene). Some of the H ligands are located in threefold hollows between Rh centers and thus mimic the orientation of atomic hydrogen adsorbed on Rh(111).

show abstract

New directions in the chemistry of dirhodium(II) compounds

Cited by 57 publications

References 0 publications

Dirhodium(II) Compounds with Bridging Thienylphosphines: Studies on Reversible P,C/P,S Coordination

Dirhodium(II) Compounds with Bridging Thienylphosphines: Studies on Reversible P,C/P,S Coordination

Unusual Chemoselective Rh^II‐Catalysed Transformations of α‐Diazocarbonyl Piperidine Cores

[Rh₇(PiPr₃)₆H₁₈][BAr^F₄]₂: A Molecular Rh(111) Surface Decorated with 18 Hydrogen Atoms

Contact Info

Product

Resources

About

New directions in the chemistry of dirhodium(II) compounds

Cited by 57 publications

References 0 publications

Dirhodium(II) Compounds with Bridging Thienylphosphines: Studies on Reversible P,C/P,S Coordination

Dirhodium(II) Compounds with Bridging Thienylphosphines: Studies on Reversible P,C/P,S Coordination

Unusual Chemoselective RhII‐Catalysed Transformations of α‐Diazocarbonyl Piperidine Cores

[Rh7(PiPr3)6H18][BArF4]2: A Molecular Rh(111) Surface Decorated with 18 Hydrogen Atoms

Contact Info

Product

Resources

About

Unusual Chemoselective Rh^II‐Catalysed Transformations of α‐Diazocarbonyl Piperidine Cores

[Rh₇(PiPr₃)₆H₁₈][BAr^F₄]₂: A Molecular Rh(111) Surface Decorated with 18 Hydrogen Atoms