Synthesis, structure, and reactivity of (. eta. sup 4 (5e)-butadienyl)ruthenium complexes: Crystal structures of CpRu = C(Ph)-. eta. sup 3 -(C(Ph)C(Ph)CH(Ph)), CpRuC(Ph) = C(Ph)-. eta. sup 2 -(C(Ph) = CH(Ph))P(OMe) sub 3 , and CpRu sub 2 (. mu. -(Z)-C(Ph) = CH(Ph))(CO) sub 2 (. eta. sup 4 -C sub 4 Ph sub 4 )
- Univ. of Bristol (England)
The chemistry of the first example of a {eta}{sup 4}(5e)-butadienyl complex is described. Reaction of (CpRu(NCMe)({eta}{sup 4}-C{sub 4}Ph{sub 4}))(BF{sub 4}) with K(BHBu{sub 3}{sup a}) affords CpRu{double bond}C(Ph)-{eta}{sup 3}-(C(Ph)C(Ph)CH(Ph)) (5), which was structurally identified by single-crystal X-ray crystallography. Compound 5 is triclinic, space group P{anti 1} (No. 2); a = 10.156 (5), b = 10.996 (5), c = 13.145 (6) {angstrom}, {alpha} = 112.12 (4), {beta} = 101.20 (4), {gamma} = 103.76 (4){degree}. The molecule contains an open-chain {eta}{sup 4}(5e)-butadienyl system, in which the CpRu fragment is double bonded to C(1) (Ru-C(1) = 1.896 (5) {angstrom}), the remaining three carbon ruthenium distances Ru-C(2) (2.204 (5) {angstrom}), Ru-C(3) (2.152 (4) {angstrom}), and Ru-C(4) (2.154 (6) {angstrom}) being appropriate for an {eta}{sup 3}-allyl system. A mechanism is proposed for the formation of 5 involving conrotatory ring-opening of an {eta}{sup 3}-cyclobutenyl intermediate carrying an endo hydrogen, which becomes a pseudo-syn hydrogen on the terminus of the C{sub 4} chain.
- OSTI ID:
- 6429153
- Journal Information:
- Organometallics; (USA), Vol. 9:5; ISSN 0276-7333
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
RUTHENIUM COMPLEXES
CRYSTAL STRUCTURE
REACTIVITY
SYNTHESIS
DATA ANALYSIS
EXPERIMENTAL DATA
MEASURING INSTRUMENTS
MEASURING METHODS
ORGANOMETALLIC COMPOUNDS
COMPLEXES
DATA
INFORMATION
NUMERICAL DATA
ORGANIC COMPOUNDS
TRANSITION ELEMENT COMPLEXES
400201* - Chemical & Physicochemical Properties