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Werner, Helmut; Feser, R.

doi:10.1016/s0022-328x(00)89216-5

Cited by 35 publications

(24 citation statements)

References 37 publications

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“…This unique regioselectivity has been attributed to the stabilizing effect of a p-benzyl interaction available only to the branched isomer 3. [2] p-Benzyl complexes of a variety of transition metals [10][11][12][13][14][15] including rhodium [16][17][18][19][20][21] have been isolated, however, there is no empirical evidence to definitively ascribe the regioselectivity in the rhodiumcatalyzed hydroboration to this interaction.…”

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confidence: 99%

Regioselectivity of the Rhodium‐Catalyzed Hydroboration of Vinyl Arenes: Electronic Twists and Mechanistic Shifts

et al. 2007

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Any substituent does it: The hydroboration of vinyl arenes with pinacol borane (HBPin) and cationic rhodium complexes selectively placed the boron proximal to the aryl rather than phenyl ring, regardless of whether this ring bears electron‐donating or electron‐withdrawing substituents. In competition experiments between styrene and various vinyl arenes, preferential hydroboration also occured at the substituted arene (see scheme). Hammett plots indicate a break in the mechanism.

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confidence: 99%

Regioselectivity of the Rhodium‐Catalyzed Hydroboration of Vinyl Arenes: Electronic Twists and Mechanistic Shifts

et al. 2007

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“…During 2 h, a change of color from deep blue to orange-yellow occurred. The 1 H NMR spectrum confirmed that both 15 [30] and 1.1-diphenyl-1-propene (16) [29] were formed; yield virtually quantitative.…”

Section: [(H 5 -C 5 H 5 )Rh(cph 2 )(Pph 3 )] (2 H)mentioning

confidence: 93%

“…After warming to room temperature, the reaction mixture was worked up as described for a); yield 30 ortho-, meta-and para-C of C 6 H 5 ), 81.6 (d, J(Rh,C) 6.4 Hz; C 5 H 5 ); elemental analysis for C 17 H 15 N 4 Rh (378.2): calcd: C 53.98,H 4.00,N 14.81;found: C 53.76,H 3.74,N 14.91.…”

Section: [(H 5 -C 5 H 5 )Rh(cph 2 )(Pph 3 )] (2 H)mentioning

confidence: 99%

Carbenerhodium Complexes of the Half-Sandwich-Type: Synthesis, Substitution, and Addition Reactions

et al. 2000

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A series of carbenerhodium(I) complexes of the general composition [(eta5-C5H5)Rh(=CRR')(L)] (2a-2i) with R = R'= aryl and L = SbiPr3 or PR3 has been prepared from the square-planar precursors trans-[RhCl(=CRR')(L)2] and NaC5H5 in excellent yields. Reaction of the triisopropylsibane derivative 2a. which contains a rather labile Rh-Sb bond, with CO, PMe3, and CNR (R = Me, CH2Ph, tBu) leads to the displacement of the SbiPr3 ligand and affords the substitution products [(eta5-C5H5)Rh(=CPh2)(L)] (3-7). In contrast, treatment of the triisopropylphosphane compound 2c with CO and CNtBu leads to the cleavage of the Rh=CPh2 bond and gives besides [(eta5-C5H5)Rh(PiPr3)(L)] (10, 12) by metal-assisted C-C coupling diphenylketene Ph2C=C=O (11) or the corresponding imine Ph2C=C=NtBu (13). While the reaction of 2a, c with C2H4 yields [(eta5-C5H5)Rh(C2H4)(L)] (14, 15) and the trisubstituted olefin Ph2C=CHCH3 (16), treatment of 2a, c with RN3 leads to the cleavage of both the Rh-EiPr3 and Rh=CPh2 bonds and gives the chelate complexes [(eta5-C5H5)Rh(kappa2-RNNNNR)] (19, 20). The substitution products 3 (L=CO) and 4 (L= PMe3) react with an equimolar amount of sulfur or selenium by addition of the chalcogen to the Rh=CPh2 bond to generate the complexes [(eta5-C5H5)Rh(kappa2-ECPh2)(L)] (21-24) with thio- or selenobenzophenone as ligand. Similarly, treatment of 3 with CuCl affords the unusual 1:2 adduct [(eta5-C5H5)(CO)Rh(mu-CPh2)(CuCl)2] (25), which reacts with NaC5H5 to form [(eta5-C5H5)(CO)Rh(muCPh2)Cu(eta5-C5H5)] (26). The molecular structures of 3 and 22 have been determined by X-ray crystallography.

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“…CpRh(PMe 3 )(C 2 H 4 ) was synthesized by literature procedures, but replacing TlCp by LiCp. 44 4-Dimethylamino-2,3,5,6 tetrafluoropyridine and 4-methoxy-2,3,5,6-tetrafluoropyridine were also synthesized by literature procedures. 45 The pyridines were additionally characterized by NMR spectroscopy and EI mass spectrometry.…”

Section: Experimental Sectionmentioning

confidence: 99%

Photochemical Reactions of Fluorinated Pyridines at Half-Sandwich Rhodium Complexes: Competing Pathways of Reaction

et al. 2013

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Irradiation of CpRh(PMe3)(C2H4) (1; Cp = η5-C5H5) in the presence of pentafluoropyridine in hexane solution at low temperature yields an isolable η2-C,C-coordinated pentafluoropyridine complex, CpRh(PMe3)(η2-C,C-C5NF4) (2). The molecular structure of 2 was determined by single-crystal X-ray diffraction, showing coordination by C3–C4, unlike previous structures of pentafluoropyridine complexes that show N-coordination. Corresponding experiments with 2,3,5,6-tetrafluoropyridine yield the C–H oxidative addition product CpRh(PMe3)(C5NF4)H (3). In contrast, UV irradiation of 1 in hexane, in the presence of 4-substituted tetrafluoropyridines C5NF4X, where X = NMe2, OMe, results in elimination of C2H4 and HF to form the metallacycles CpRh(PMe3)(κ2-C,C-CH2N(CH3)C5NF3) (4) and CpRh(PMe3)(κ2-C,C-CH2OC5NF3) (5), respectively. The X-ray structure of 4 shows a planar RhCCNC-five-membered ring. Complexes 2–5 may also be formed by thermal reaction of CpRh(PMe3)(Ph)H with the respective pyridines at 50 °C.

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Basische metalle

Cited by 35 publications

References 37 publications

Regioselectivity of the Rhodium‐Catalyzed Hydroboration of Vinyl Arenes: Electronic Twists and Mechanistic Shifts

Regioselectivity of the Rhodium‐Catalyzed Hydroboration of Vinyl Arenes: Electronic Twists and Mechanistic Shifts

Carbenerhodium Complexes of the Half-Sandwich-Type: Synthesis, Substitution, and Addition Reactions

Photochemical Reactions of Fluorinated Pyridines at Half-Sandwich Rhodium Complexes: Competing Pathways of Reaction

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