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Chemical transformations on phosphido-bridged clusters. Reactions of the. mu. /sub 3/-eta/sup 3/-allenyl complex Ru/sub 3/(CO)/sub 8/. mu. /sub 3/-eta/sup 3/-CH/sub 2/CC(i-Pr)/(. mu. -PPh/sub 2/). Reversible CO addition, adduct formation with P(OMe)/sub 3/, hydrogenation, and alkyne insertion

Journal Article · · Organometallics; (United States)
DOI:https://doi.org/10.1021/om00091a021· OSTI ID:7256208
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In a preceding paper the authors reported the synthesis of the allenyl cluster Ru/sub 3/(CO)/sub 8//..mu../sub 3/-eta/sup 3/-CH/sub 2/CC(i-Pr)/(..mu..-PPh/sub 2/) (1) via methylene (CH/sub 2/) addition to the acetylide Ru/sub 3/(CO)/sub 6/(..mu..-CO)/sub 2//..mu../sub 3/-eta/sup 2/-C==C(i-Pr)/(..mu..-PPh/sub 2/) (2). Like its isoelectronic 48-electron acetylide counterpart, 2, cluster 1 behaves as if it is coordinativley unsaturated, adding nucleophiles with great facility at ambient temperatures. Lewis base additions to clusters without ligand dissociation have been observed recently for several other systems, but only in very few cases have the scope and synthetic implications of such reactivity been explored. Here they report a series of reactions of the cluster 1 including reversible CO addition, formation of a phosphite adduct, a novel hydrogenation of the unsaturated ligand, and a series of alkyne insertions leading to hydrocarbon chain extension.

Research Organization:
Univ. of Waterloo, Ontario (Canada)
OSTI ID:
7256208
Journal Information:
Organometallics; (United States), Journal Name: Organometallics; (United States) Vol. 7:1; ISSN ORGND
Country of Publication:
United States
Language:
English

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Chemical transformations on phosphido-bridged clusters. Methyne, methylene transfer, and ketene forming reactions involving the. mu. methylene cluster Ru/sub 3/(CO)/sub 7/(. mu. -CH/sub 2/)/. mu. /sub 3/-eta/sup 3/-CH/sub 2/ =C=C(i-Pr)/(. mu. -PPh/sub 2/). X-ray structures of (. mu. -H)Ru/sub 3/(CO)/sub 7//. mu. /sub 3/-eta/sup 4/-CH=C(i-Pr)C=CH/sub 2//(. mu. -PPH/sub 2/) and Ru/sub 3/(CO)/sub 6/(. mu. -CO)/. mu. /sub 3/-eta/sup 4/-CH/sub 2/=C(i-Pr)C=CH/sub 2//(PPh/sub 3/)(. mu. -PPH/sub 2/)
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Related Subjects

01 COAL, LIGNITE, AND PEAT
010408 -- Coal
Lignite
& Peat-- C1 Processes-- (1987-)
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
ADDUCTS
CARBON COMPOUNDS
CARBON MONOXIDE
CARBON OXIDES
CARBONYLS
CHALCOGENIDES
CHEMICAL REACTIONS
COMPLEXES
DATA
EXPERIMENTAL DATA
HYDROGENATION
INFORMATION
LIGANDS
NUMERICAL DATA
OXIDES
OXYGEN COMPOUNDS
PHOSPHINES
PHOSPHORUS COMPOUNDS
RUTHENIUM COMPLEXES
TRANSITION ELEMENT COMPLEXES