Reactions of (C sub 5 Me sub 5 )Rh(PMe sub 3 )(R)H with electrophiles. Insertion of unsaturated molecules into activated carbon-hydrogen bonds

Journal Article · Sun Dec 31 23:00:00 EST 1989 · Organometallics; (USA)

DOI:https://doi.org/10.1021/om00115a026· OSTI ID:6661536

Jones, W D; Chandler, V L; Feher, F J ^[1]

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1. Univ. of Rochester, NY (USA)

The complexes (C{sub 5}Me{sub 5})Rh(PMe{sub 3})(aryl)H (aryl = C{sub 6}H{sub 5}, 2,6-C{sub 6}H{sub 3}Me{sub 2}) are found to react with several electrophiles. Treatment with CS{sub 2} gives two products, the major species resulting from the elimination of benzene and formation of (C{sub 5}Me{sub 5})Rh(PMe{sub 3})(CS{sub 2}). The minor product is formed by insertion into the Rh-H bond to give (C{sub 5}Me{sub 5})Rh(PMe{sub 3})(Ph)(SCH=S). Reaction of the aryl hydride complex with PhNCS gives only the insertion product (C{sub 5}Me{sub 5})Rh(PMe{sub 3})(Ph)(SCH=NPh). These two sulfur-bound derivatives react with either aniline of H{sub 2}S, respectively, to give (C{sub 5}Me{sub 5})Rh(PMe{sub 3})(Ph)(SCH(SH)(NHPh)), which cleaves during isolation to give (C{sub 5}Me{sub 5})Rh(PMe{sub 3})(Ph)(SH) and PhNHCH=S. Reaction of the aryl hydride complex with dimethyl acetylenedicarboxylate results in insertion of acetylene into the Rh-H bond, producing a mixture of the cis and trans vinyl complexes. HI cleaves the rhodium-aryl bond, and iodine induces both elimination of substituted styrene and iodination of the metal-xylyl bond in the cis complex. Treatment of the trans isomer with HI also cleaves the Rh-aryl bond, and iodine gives a mixture of products. The methyl complex (C{sub 5}Me{sub 5})Rh(PMe{sub 3})(CH{sub 3})H reacts with dimethyl acetylenedicarboxylate to give a mixture of cis and trans vinyl methyl complexes. Addition of iodine results in the formation of methyl iodide and (C{sub 5}Me{sub 5})Rh(PMe{sub 3})(C(COOMe)=CH(COOOMe))I. cis-(C{sub 5}Me{sub 5})Rh(PMe{sub 3})(2,6-C{sub 6}H{sub 3}Me{sub 2})(C(COOMe)=CH(COOOMe)) crystallizes in the triclinic space group P{bar 1} with a = 8.928 (5) {angstrom}, b = 19.111 (4) {angstrom}, c = 8.590 (2) {angstrom}, {alpha} = 94.21 (2){degree}, {beta} = 111.86 (4){degree}, {gamma} = 94.08 (3){degree}, V = 1348.9 (1.8) {angstrom}{sup 3}, and Z = 2.

• DOE Contract Number: FG02-86ER13569
• OSTI ID: 6661536
• Journal Information: Organometallics; (USA), Journal Name: Organometallics; (USA) Vol. 9:1; ISSN 0276-7333; ISSN ORGND
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400200* -- Inorganic
Organic
& Physical Chemistry
CARBON
CHEMICAL BONDS
CHEMICAL REACTIONS
COMPLEXES
CRYSTAL STRUCTURE
DATA
DATA ANALYSIS
ELEMENTS
EXPERIMENTAL DATA
HYDROCARBONS
HYDROGEN
INFORMATION
MEASURING INSTRUMENTS
MEASURING METHODS
NONMETALS
NUMERICAL DATA
ORGANIC COMPOUNDS
ORGANOMETALLIC COMPOUNDS
REDOX REACTIONS
RHODIUM COMPLEXES
TRANSITION ELEMENT COMPLEXES