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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/)

Journal Article · · Organometallics; (United States)
DOI:https://doi.org/10.1021/om00091a020· OSTI ID:7148476
; ; ; ; ;
The ..mu..-methylene cluster Ru/sub 3/(CO)/sub 7/(..mu..-CH)/..mu../sub 3/-eta/sup 3/-CH/sub 2/=C=C(i-Pr))/(..mu..-PPh/sub 2/) (2) synthesized from Ru/sub 3/-(CO)/sub 8//..mu..=eta/sup 3/-CH/sub 2/=C=C(i-Pr)/(..mu..-PPh/sub 2/) (1) via reaction with diazomethane, CH/sub 2/N/sub 2/, displays a remarkable reactivity associated with the ..mu..-CH/sub 2/ group under mild conditions. Slow isomerization of 2 to the 2-isopropyl-1,3-butadienediyl cluster (..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/) (3) (crystal data: triclinic, space group P anti 1, a = 9.333 (2) A, b = 10.200 (1) A, c = 16.297 (2) A, ..cap alpha.. = 87.25 (1)/sup 0/, ..beta.. = 83.26 (1)/sup 0/, ..gamma.. = 64.29 (1)/sup 0/, Z = 2, R = 0.25, R/sub w/ = 0.029 on 5899 observed reflections) occurs under nitrogen. Cluster 3 contains a triangular Ru/sub 3/ core with ..mu..-PPh/sub 2/ and ..mu..-H groups on one edge and a four-carbon hydrocarbyl ligand derived from a CH fragment of the ..mu..-methylene bride and the allenyl ligand of 2. Under an atmosphere of CO and in the presence of methanol complex 2 yields the open allenyl cluster Ru/sub 3/(CO)/sub 9//..mu../sub 3/-eta/sup 3/-CH/sub 2/=C=C(i-Pr)/(..mu..-PPh/sub 2/) (5) and methyl acetate, both of which were characterized spectroscopically.
Research Organization:
Univ. of Waterloo, Ontario (Canada)
OSTI ID:
7148476
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. 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 · Thu Dec 31 23:00:00 EST 1987 · Organometallics; (United States) · OSTI ID:7256208
Interaction of (. mu. -H)/sub 2/Ru/sub 4/(CO)/sub 12/ with diphosphines in the presence of trimethylamine n-oxide. X-ray crystal structure analyses of (. mu. -H)/sub 4/Ru/sub 4/(CO)/sub 10/(. mu. -)Ph/sub 2/P(CH/sub 2/)/sub n/PPh/sub 2/)) (n = 1, 3, 4), (. mu. -H/sub 4/Ru/sub 4/(CO)/sub 10/(. mu. -)Ph/sub 2/PCH/sub 2/CH(CH/sub 3/)PPh/sub 2/)), and (. mu. -H)/sub 2/Ru/sub 4/(CO)/sub 10/()Ph/sub 2/PCH/sub 2/CH(CH/sub 3/PPh/sub 2/))
Journal Article · Tue Mar 24 23:00:00 EST 1987 · Inorg. Chem.; (United States) · OSTI ID:6674068
Photochemistry of (/eta//sup 3/-C/sub 3/H/sub 5/)Ru(CO)/sub 3/Br: Spectroscopic evidence for the intermediates (/eta//sup 3/-C/sub 3/H/sub 5/)Ru(CO)/sub 2/Br and ((/eta//sup 3/-C/sub 3/H/sub 5/)Ru(CO)/sub 2/(/mu/-Br))/sub 2/
Journal Article · Mon Aug 01 00:00:00 EDT 1988 · Organometallics; (United States) · OSTI ID:5775358

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
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ALKENES
BOND ANGLE
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CARBONYLS
CHEMICAL REACTIONS
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ORGANIC COMPOUNDS
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RUTHENIUM COMPLEXES
SCATTERING
TRANSITION ELEMENT COMPLEXES
X-RAY DIFFRACTION