Výsledky vyhledávání - "Peter Dr. Schwab"

Carbenerhodium(I) complexes of the half-sandwich-type: reactions with electrophiles

Autor: Peter Dr. Schwab, Helmut Werner, Matthias Laubender, Elke Bleuel

Publikováno v: Journal of the Chemical Society, Dalton Transactions. :266-273

The reaction of the carbenerhodium(I) complexes [(η5-C5H5)Rh(CR2)(L)] (R = aryl) with HX (X = Cl, CF3CO2) led, depending on the size and donor properties of the ligand L, to two different types of products. While compounds 1, 2 with R = Ph and L = C

Externí odkaz: https://explore.openaire.eu/search/publication?articleId=doi_________::4e7e91fe80023e1c6d36f0c91c8b66f7
https://doi.org/10.1039/b008354m

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Reaction of the dimeric bis(olefin)rhodium(I) compounds [RhCl(olefin) 2 ] 2 [olefinC 8 H 14 (2), C 2 H 4 (5)] with As i Pr 3 and Sb i Pr 3 gives mono‐ and dinuclear olefin(arsane) and olefin(stibane) complexes [RhCl(olefin)(E i Pr 3 )] 2 [olefinC 8 H 14 (3, 4), C 2 H 4 (6, 7)] and trans ‐[RhCl(C 2 H 4 )(E i Pr 3 ) 2 ] (8, 9). Treatment of 8 and 9 with CO, H 2 , and CPh 2 N 2 leads to the displacement of the ethylene ligand with formation of the corresponding carbonyl (10, 11), dihydrido (12, 13), and diazoalkane (14) rhodium derivatives. In solution, compound 14 loses CPh 2 to give trans ‐[RhCl(N 2 )(As i Pr 3 ) 2 ] (15). The alkyne complexes trans ‐[RhCl(HCC̊)(As i Pr 3 ) 2 ] (16–18), which are prepared either from 8 or [RhH 2 Cl(As i Pr 3 ) 2 ] (12) and HCC̊ (RH, Ph, CO 2 Me), rearrange in solution to produce the vinylidenerhodium isomers trans ‐[RhCl(CCHR)(As i Pr 3 ) 2 ] (19–21). Reaction of 8 with HCCMe and HCC t Bu leads directly to the vinylidene complexes 22, 23. Compound 8 reacts with excess propyne, but–2‐yne, or 2,2–dimethylpent–2‐yne to give the rhodium allenes trans ‐[RhCl(η 2 ‐CH 2 CCHR)(As i Pr 3 ) 2 ] (25–27) in nearly quantitative yields. With DCCMe as a substrate, it is shown that two propyne molecules are involved in the rearrangement to generate the coordinated allene. The crystal and molecular structure of trans ‐[RhCl(η 2 ‐CH 2 CCH 2 )(As i Pr 3 ) 2 ] (27) has been determined

Autor: Peter Dr. Schwab, Justin Wolf, Helmut Werner, Norbert Mahr

Publikováno v: Chemische Berichte. 125:2641-2650

Externí odkaz: https://explore.openaire.eu/search/publication?articleId=doi_________::00bd580e4b7aff43122887a72b5e07cd
https://doi.org/10.1002/cber.19921251204

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Carbenerhodium complexes of the half-sandwich-type: synthesis, substitution, and addition reactions

Autor: Norbert Mahr, Justin Wolf, Bettina Windmüller, Helmut Werner, Peter Dr. Schwab, Elke Bleuel

Publikováno v: Chemistry (Weinheim an der Bergstrasse, Germany). 6(24)

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. R

Externí odkaz: https://explore.openaire.eu/search/publication?articleId=doi_dedup___::11c1876966619c1d4f49bfd45c4abd33
https://pubmed.ncbi.nlm.nih.gov/11192078

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