Rhodium complexes of C-bonded pyridines: Synthesis and X-ray structure of (C sub 5 Me sub 5 Rh(Me)(CO) l brace 3-C sub 5 H sub 4 N-Rh(CO) sub 2 Cl r brace ), a complex containing 3-pyridyl C,N-bridging Rh(I) and Rh(III)

Journal Article · Mon Jan 01 04:00:00 EST 1990 · Organometallics; (USA)

DOI:https://doi.org/10.1021/om00115a021· OSTI ID:6654700

Fanizzi, F P; Sunley, G J; Wheeler, J A; Adams, H; Bailey, N A; Maitlis, P M ^[1]

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1. The University, Sheffield (England)

The reaction of (C{sub 5}Me{sub 5}RhMe{sub 2}(Me{sub 2}SO)) with 2-, 3-, and 4-pyridinecarboxyaldehyde gave the appropriately substituted (C{sub 5}Me{sub 5}Rh(Me)(CO)(x-C{sub 5}H{sub 4}N)) (2, x = 2-4) in 80-90% yields; (C{sub 5}Me{sub 5}Ir(Me)(CO)(4-C{sub 5}H{sub 4}N)) was prepared analogously. The 2- and 3-pyridyl complexes were readily quaternized by reaction with MeI to give (C{sub 5}Me{sub 5}Rh(Me)(CO)(x-C{sub 5}H{sub 4}NMe))I, (x = 2, 3), but the (4-pyridyl)rhodium complex underwent coupling to give 1,4-dimethylpyridinium iodide and (C{sub 5}Me{sub 5}Rh(CO)Me(I)). The products from the last reaction with CD{sub 3}I were (C{sub 5}Me{sub 5}Rh(CO)Cd{sub 3}(I)) and (4-CH{sub 3}C{sub 5}H{sub 4}NCD{sub 3}{sup +}){sup {minus}}. On reaction of (C{sub 5}Me{sub 5}Rh(Me)(CO)(4-C{sub 5}H{sub 4}N)) with other electrophiles (H{sup +}BF{sub 4}{sup {minus}}, Et{sub 3}O{sup +}BF{sub 4}{sup {minus}}), evidence for the formation of unstable salts, (C{sub 5}Me{sub 5}Rh(Me)(CO)(4-C{sub 5}H{sub 4}NH)){sup +} and (C{sub 5}Me{sub 5}Rh(Me)(CO)(4-C{sub 5}H{sub 4}NEt)){sup +}, was obtained. In contrast, the complex (C{sub 5}Me{sub 5}Rh(Me)(CO)(4-C{sub 5}H{sub 4}N)) reacted with methyl iodide to give the stable (C{sub 5}Me{sub 5}Ir(Me)(CO)(4-C{sub 5}H{sub 4}NMe)){sup +}I{sup {minus}}. (C{sub 5}Me{sub 5}Rh(Me)(CO)(x-C{sub 5}H{sub 4}N)) (x = 3, 4) reacted with (Rh{sub 2}(CO){sub 4}Cl{sub 2}) to give the novel dinuclear adducts (C{sub 5}Me{sub 5}Rh(Me)(CO){l brace}x-C{sub 5}H{sub 4}NRh(CO){sub 2}Cl{r brace}), in which a 3- or a 4-pyridyl bridges Rh(III) and Rh(I). An X-ray determination of (C{sub 5}Me{sub 5}Rh(Me)(CO){l brace}3-C{sub 5}H{sub 4}NRh(CO){sub 2}Cl{r brace}) confirmed the structure.

• OSTI ID: 6654700
• 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
AZINES
COMPLEXES
CRYSTAL STRUCTURE
DATA
DATA ANALYSIS
EXPERIMENTAL DATA
HETEROCYCLIC COMPOUNDS
INFORMATION
MEASURING INSTRUMENTS
MEASURING METHODS
NUMERICAL DATA
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
ORGANOMETALLIC COMPOUNDS
PYRIDINES
RHODIUM COMPLEXES
SYNTHESIS
TRANSITION ELEMENT COMPLEXES