Solid-state structure and fluxional solution behavior of the ambident organometallic nucleophiles (. eta. sup 3 -C sub 7 H sub 7 )M(CO) sub 3 sup minus (M = Ru, Os)

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

DOI:https://doi.org/10.1021/om00115a028· OSTI ID:6654618

Astley, S T; Takats, J ^[1]; Huffman, J C; Streib, W E ^[2]

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1. Univ. of Alberta, Edmonton (Canada)
2. Indiana Univ., Bloomington (USA)

The cycloheptatrienyl carbonyl anions (C{sub 7}H{sub 7})M(CO){sub 3}{sup {minus}} (M = Ru, 1b; M = Os, 1c) have been isolated and structurally characterized as their Ph{sub 4}As{sup +} salts. Both 1b and 1c crystallize in the centrosymmetric space group P{bar 1} with two molecules per unit cell. For 1b: a = 12.308 (4) {angstrom}, b = 12.017 (5) {angstrom}, c = 11.326 (4) {angstrom}, {alpha} = 71.18 (2){degree}, {beta} = 80.93 (2){degree}, {gamma} = 90.15 (2){degree}. For 1c: a = 12.314 (2) {angstrom}, b = 12.025 (2) {angstrom}, c = 11.331 (2) {angstrom}, {alpha} = 71.12 (2){degree}, {beta} = 80.87 (2){degree}, {gamma} = 90.08{degree}. The structures were refined to R(F) = 0.0567 and 0.0268 and R{sub w}(F) = 0.0575 and 0.0278 for 3,686 and 3,905 reflections with F > 3.0{sigma}(F) for 1b and 1c, respectively. In both cases the seven-membered ring is coordinated to the metal in an {eta}{sup 3} fashion. The low-temperature-limiting {sup 1}H and {sup 13}C NMR spectra of 1c have been obtained and show that the same bonding mode is also adopted in solution. A comparison of the spectroscopic, structural, and chemical properties for the series of complexes (C{sub 7}H{sub 7})M(CO){sub 3}{sup {minus}} (M = Fe, Ru, Os) is made and explained in terms of increasing metal basicity upon descending the triad.

• OSTI ID: 6654618
• 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
COMPLEXES
CRYSTAL STRUCTURE
DATA
DATA ANALYSIS
EXPERIMENTAL DATA
INFORMATION
MEASURING INSTRUMENTS
MEASURING METHODS
NMR SPECTRA
NUMERICAL DATA
ORGANIC COMPOUNDS
ORGANOMETALLIC COMPOUNDS
OSMIUM COMPLEXES
RUTHENIUM COMPLEXES
SPECTRA
TRANSITION ELEMENT COMPLEXES