sigma. -acetlyide complexes of rhodium(I), rhodium(II), and rhodium(III). Correlation between electrochemical (E degree prime ) and spectroscopic (. Delta. nu. (C=C)) parameters and d. pi. (metal) yields. pi. * (acetylide) transfer

Journal Article · Thu Feb 01 04:00:00 EST 1990 · Organometallics; (USA)

DOI:https://doi.org/10.1021/om00116a011· OSTI ID:7245895

Bianchini, C; Meli, A; Peruzzini, M; Vacca, A ^[1]; Laschi, F; Zanello, P ^[2]; Ottaviani, F M ^[3]

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1. Istituto per lo Studio della Stereochimica ed Energetica dei Composti di Coordinazione, Firenze (Italy)
2. Universita de Siena (Italy)
3. Universita di Firenze (Italy)

Terminal acetylide complexes of rhodium(II) and rhodium(III) with the tripodal polyphosphine ligands N(CH{sub 2}CH{sub 2}PPh{sub 2}){sub 3} (NP{sub 3}) and P(CH{sub 2}CH{sub 2}PPh{sub 2}){sub 3} (PP{sub 3}) have been synthesized either by controlled-potential coulometry or by chemical oxidation of the Rh(I) neutral {sigma}-acetylide compounds ((L)Rh(C{triple bond}CR)) (L = NP{sub 3}, R = Ph, CO{sub 2}Et; L = PP{sub 3}, R = Ph, CO{sub 2}Et, CHO). All of the compounds undergo electron-transfer reactions that encompass the Rh(I), Rh(II), and Rh(III) oxidation states of the metal. The characterization has been carried out by IR, NMR, and ESR techniques. The presence of a significant d{pi} (metal) {yields} {pi} (acetylide) interaction in the HOMO is diagnosed by comparing and contrasting either the stretching frequencies {nu}(C{triple bond}C) within the members of the ((L)Rh(C{triple bond}CR)){sup n+} family (n = 0-2) or the redox potentials E{degree}{prime} within the more numerous ((L)RhX) family (X = C1, H, C{triple bond}CR, CN, CO).

• OSTI ID: 7245895
• Journal Information: Organometallics; (USA), Journal Name: Organometallics; (USA) Vol. 9:2; ISSN 0276-7333; ISSN ORGND
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201 -- Chemical & Physicochemical Properties
400400* -- Electrochemistry
CALCULATION METHODS
CHEMISTRY
COMPLEXES
DATA
DATA ANALYSIS
ELECTROCHEMISTRY
ELECTRON TRANSFER
EXPERIMENTAL DATA
INFORMATION
MEASURING INSTRUMENTS
MEASURING METHODS
NMR SPECTRA
NUMERICAL DATA
PHOSPHIDES
PHOSPHORUS COMPOUNDS
PNICTIDES
REFRACTORY METAL COMPOUNDS
RHODIUM COMPLEXES
RHODIUM COMPOUNDS
RHODIUM PHOSPHIDES
SPECTRA
SYNTHESIS
TRANSITION ELEMENT COMPLEXES
TRANSITION ELEMENT COMPOUNDS