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/)

Nucciarone, D; Taylor, N J; Carty, A J; Tiripicchioi, A; Camellini, M; Sappa, E

doi:10.1021/om00091a020

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 · Thu Dec 31 23:00:00 EST 1987 · Organometallics; (United States)

DOI:https://doi.org/10.1021/om00091a020· OSTI ID:7148476

Nucciarone, D; Taylor, N J; Carty, A J; Tiripicchioi, A; Camellini, M; Sappa, E

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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