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 )

Crocker, M; Green, M; Nagle, K R; Orpen, A G; Neumann, H P; Morton, C E; Schaverien, C J

doi:10.1021/om00119a012

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 )

Journal Article · Tue May 01 00:00:00 EDT 1990 · Organometallics; (USA)

DOI:https://doi.org/10.1021/om00119a012· OSTI ID:6429153

Crocker, M; Green, M; Nagle, K R; Orpen, A G; Neumann, H P; Morton, C E; Schaverien, C J ^[1]

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), Journal Name: Organometallics; (USA) Vol. 9:5; ISSN 0276-7333; ISSN ORGND

Country of Publication:: United States

Language:: English

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Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
COMPLEXES
CRYSTAL STRUCTURE
DATA
DATA ANALYSIS
EXPERIMENTAL DATA
INFORMATION
MEASURING INSTRUMENTS
MEASURING METHODS
NUMERICAL DATA
ORGANIC COMPOUNDS
ORGANOMETALLIC COMPOUNDS
REACTIVITY
RUTHENIUM COMPLEXES
SYNTHESIS
TRANSITION ELEMENT COMPLEXES

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