Iridium [eta][sup 4]-1,5-cyclooctadiene and 1,2-[eta][sup 2],6-[sigma]-cycloocta-1,4-dienyl complexes. Deprotonation of coordinated 1,5-cyclooctadiene by strong and weak bases
- Purdue Univ., West Lafayette, IN (United States)
The reaction of [Ir([eta][sup 4]-1,5-cyclooctadiene)Cl][sub 2] with 2 equiv of triphos [(Ph[sub 2]PCH[sub 2]CH[sub 2])[sub 2]PPh] in methylene chloride yields [Ir(triphos)([eta][sup 4]-1,5-cyclooctadiene)][Cl] (1), which upon reaction with various bases [KOH, NaOCH[sub 3], NaOC[sub 6]H[sub 5], NaOC[sub 6]H[sub 4]-p-CH[sub 3], NaOC[sub 6]H[sub 4]-p-C(CH[sub 3])[sub 3], N(C[sub 2]H[sub 5])[sub 3], pyridine, N,N,N',N'-tetramethyl-1,8-naphthalenediamine (Proton Sponge)] in tetrahydrofuran solutions affords the neutral deprotonated complex, Ir(triphos)(1,2-[eta][sup 2],6-[sigma]-cycloocta-1,4-dienyl) (2). X-ray structure determinations of 1 and 2 were undertaken. Complex 1 crystallizes in the monoclinic space group P2[sub 1]/c with a = 15.165(2) A, b = 10.791(2) A, c = 23.488(2) A, V = 3843(2) A[sup 3], Z = 4, and D[sub calc] = 1.535 g/cm[sub 3]. The structure was refined to R = 0.029 and R[sub w] = 0.038 for 428 variables and 4043 observations. Complex 2 crystallizes in monoclinic space group Cc with a = 9.5782(8) A, b = 39.313(5) A, c = 11.252(2) A, V = 3911(4) A[sup 3], Z = 4, and D[sub calc] = 1.560 g/cm[sup 3]. The structure was refined to R = 0.027 and R[sub w] = 0.034 for 425 variables and 2301 observations. The mechanism of formation of 2 by deprotonation of 1 is discussed. 7 refs., 2 figs., 7 tabs.
- DOE Contract Number:
- FG22-89PC89770
- OSTI ID:
- 6258993
- Journal Information:
- Organometallics; (United States), Vol. 12:6; ISSN 0276-7333
- Country of Publication:
- United States
- Language:
- English
Similar Records
Tungsten(VI) hexahydride complexes supported by chelating triphosphine ligands: Protonation to give [eta][sup 2]-dihydrogen complexes and catalytic dehydrogenation of cyclooctane to cyclooctene
Polyoxoanion-supported catalyst precursors. Synthesis and characterization of the iridium(I) and rhodium(I) precatalysts [(n-C{sub 4}H{sub 9}){sub 4}N]{sub 5}Na{sub 3}[(1,5-COD)M{center_dot}P{sub 2}W{sub 15}Nb{sub 3}O{sub 62}] (M = Ir, Rh)
Related Subjects
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
IRIDIUM COMPLEXES
CHEMICAL REACTIONS
CRYSTALLOGRAPHY
BASES
EXPERIMENTAL DATA
LIGANDS
MASS SPECTROSCOPY
METHYLENE CHLORIDE
NUCLEAR MAGNETIC RESONANCE
ORGANOMETALLIC COMPOUNDS
PHOSPHORUS COMPOUNDS
X-RAY DIFFRACTION
COHERENT SCATTERING
COMPLEXES
DATA
DIFFRACTION
INFORMATION
MAGNETIC RESONANCE
NUMERICAL DATA
ORGANIC CHLORINE COMPOUNDS
ORGANIC COMPOUNDS
ORGANIC HALOGEN COMPOUNDS
RESONANCE
SCATTERING
SPECTROSCOPY
TRANSITION ELEMENT COMPLEXES
400201* - Chemical & Physicochemical Properties
400102 - Chemical & Spectral Procedures